CN104807773B - A kind of method that organic matter in fluid sample carries out examination - Google Patents
A kind of method that organic matter in fluid sample carries out examination Download PDFInfo
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Abstract
The invention discloses a kind of method that organic matter in fluid sample carries out examination, fluid sample is analyzed including three-dimensional fluorescence spectrum method and near infrared spectroscopy is respectively adopted, to determine whether the fluid sample containing organic matter and determines the species of the organic matter, wherein, the method that fluid sample is analyzed is included using near infrared spectroscopy：Fluid sample is supported on microporous barrier, and when fluid sample contains water, the water on removing microporous barrier；The microporous barrier that will be obtained is placed in carries out near-infrared spectrum analysis in infrared spectrometer, the microporous barrier includes matrix and the grafted moiety being grafted on matrix, described matrix is polyethylene, polypropylene or ethylene propylene copolymer, and the grafted moiety is selected from the group shown in Formulas I and the group shown in Formula II.The method can effectively deduct the interference information that the water in sample is produced when near-infrared spectrum analysis are carried out to liquid, aqueous sample, be particularly well-suited to carry out rapid screening to the organic matter in water.。
Description
Technical field
The present invention relates to a kind of method that organic matter in fluid sample carries out examination.
Background technology
In the last few years, as industrialization and Development of China's Urbanization are quickly propelled, China's sudden water pollution event takes place frequently.For
Urban drinking water water quality safety during ensureing water source burst pollution, to water system whole process implementation water quality monitoring, to sudden
Pollutant quickly recognized, is the key that water purification plants successfully tackle sudden water pollution, and it is fine to be that urban water supply is carried out
Change management and improve the basis of water supply emergency capability, be the key link for establishing and improve drinking water safety security system.Supply at present
The conventional water quality detection system of water system is mainly included in the detection of line instrument and test in laboratory.However, due to on-line checking bar
The limitation of part, on-line monitoring project is general all excessively simple, is limited only to some physical and chemical indexes, it is difficult to for actual water quality monitoring is carried
For enough supports；Test in laboratory can realize the monitoring of more complete and accurate water quality index, but exist at sample
The problem that reason is complicated, analysis time is long, it is also difficult to meet the requirement of quick identification pollutant during burst pollution.Therefore, compel to be essential
Research and develop emergent rapid water quality supervision survey technology.
Near-infrared spectrum technique (FT-NIR) is a kind of high-new analytical technology for developing rapidly in recent years, with it is easy,
Quickly, it is inexpensive, pollution-free, to sample without destruction and the advantages of simultaneous determination of multiponents can be realized.Near infrared light is a kind of
(or wave number is in 12820-4000cm in 780-2526nm for wavelength-1) in the range of electromagnetic wave, near infrared spectrum is because molecule shakes
What dynamic anharmonicity was produced when making molecular vibration from ground state to high energy order transition, mainly reflect C-H, O-H, N-H and S-H
Deng the information of chemical bond.Compound and its mixing of most species can be quickly determined by near infrared spectroscopic method
Thing, and the measure of organic sample to nearly all states of matter can be realized.
But, in the near infrared spectrum qualitative and quantitative analysis of Aquo System, the near infrared absorption of water is far longer than it
The absorption of its test substance, aquagenic interference information can significantly reduce the precision of near-infrared spectrum analysis, so as to cannot lead to
Near infrared spectrum is crossed to parse functional group.
Therefore, in the near-infrared spectrum analysis of water-bearing organic sample, how to deduct the interference information that is caused by water into
The difficult point and emphasis of breakthrough are needed for near-infrared spectral analysis technology.
In addition, for near-infrared spectrum analysis, appropriate method for making sample is that near-infrared spectrum analysis are just firmly believed
The key of breath.At present, when near-infrared spectrum analysis are carried out to fluid sample, liquid sample is typically mounted in sample cell
In carry out liquid phase near-infrared spectrum analysis, but the bubble in the thickness and sample of sample cell also can produce shadow to analysis result
Ring.
The content of the invention
It is an object of the invention to provide a kind of method that organic matter in fluid sample carries out examination, the method is right
When aqueous specimen carries out near-infrared analysis, the interference information caused by water can be effectively deducted, overcome existing near infrared light
Analysis of spectrum is difficult to deduct the interference information caused by water, and then is difficult the deficiency being analyzed to aqueous specimen such that it is able to logical
The organic pollution crossed in near-infrared spectral analytical method rapid screening water.Meanwhile, the method by near infrared spectroscopy with it is three-dimensional
Fluorescent spectrometry is combined, and is obtained in that more accurate screening results.
The invention provides a kind of method that organic matter in fluid sample carries out examination, the method includes being respectively adopted
Three-dimensional fluorescence spectrum method and near infrared spectroscopy are analyzed to fluid sample, whether to differentiate the fluid sample containing organic matter,
And determine the species of the organic matter in when containing organic matter,
Wherein, the method that fluid sample is analyzed is included using near infrared spectroscopy：Fluid sample is supported on micro-
On pore membrane, and when the fluid sample contains water, the water on removing microporous barrier；The microporous barrier that will be obtained is placed in infrared spectrometer
In carry out near-infrared spectrum analysis,
The microporous barrier includes matrix and grafting at least one grafted moiety on the matrix, and described matrix is poly-
Ethene, polypropylene or ethylene-propylene copolymer, the grafted moiety are selected from the group shown in Formulas I and the group shown in Formula II,
In Formulas I, R1It is C8-C20Straight or branched alkyl；
In Formula II, R2And R3Respectively hydrogen or C1-C20Straight or branched alkyl.
The method of the present invention when near-infrared spectrum analysis are carried out to liquid, aqueous sample, in can effectively deducting sample
Water produce interference information such that it is able to improve the validity and accuracy of the near-infrared spectrum analysis of liquid, aqueous sample.
The method of the present invention is particularly well-suited to the organic matter in water suitable for being analyzed to various aqueous organic matters
Carry out rapid screening.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the atlas of near infrared spectra that test case 1 is obtained.
Fig. 2 is the first derivative spectrum figure that test case 1 is obtained.
Fig. 3 is the atlas of near infrared spectra that test comparison example 1 is obtained.
Fig. 4 is the first derivative spectrum figure that test comparison example 1 is obtained.
Fig. 5 is the atlas of near infrared spectra that test comparison example 2 is obtained.
Fig. 6 is the first derivative spectrum figure that test comparison example 2 is obtained.
Fig. 7 is the atlas of near infrared spectra that test case 2 is obtained.
Fig. 8 is the first derivative spectrum figure that test case 2 is obtained.
Fig. 9 is the standard items cluster result that (I-1) is obtained in the near-infrared spectrum analysis of embodiment 1, to be scored at front two
Principal component load diagram.
Figure 10 is the atlas of near infrared spectra of the sample that embodiment 1 (I-2) is obtained.
Figure 11 is the first derivative spectrum figure of the atlas of near infrared spectra shown in Figure 10.
Figure 12 is the test result that embodiment 1 (I-3) is obtained, to be scored at the load diagram of the principal component of front two.
Figure 13 is the standard items cluster result that (II-1) is obtained during the three-dimensional fluorescence spectrum of embodiment 1 is analyzed, before being scored at
The load diagram of the principal component of two.
Figure 14 is the three-dimensional fluorescence spectrum figure of the sample that embodiment 1 (II-2) is obtained.
Figure 15 is the test result that embodiment 1 (II-3) is obtained, to be scored at the load diagram of the principal component of front two.
Figure 16 is the standard items cluster result that (III-1) is obtained in the ultraviolet spectral analysis of embodiment 1, to be scored at front two
Principal component load diagram.
Figure 17 is the ultraviolet spectrogram of the sample that embodiment 1 (III-2) is obtained.
Figure 18 is the test result that embodiment 1 (III-3) is obtained, to be scored at the load diagram of the principal component of front two.
Specific embodiment
The invention provides a kind of method that organic matter in fluid sample carries out examination, the method includes being respectively adopted
Three-dimensional fluorescence spectrum method and near infrared spectroscopy are analyzed to fluid sample, whether to differentiate the fluid sample containing organic matter,
And the species of the organic matter is determined in when containing organic matter.
The species of organic matter of the present invention for that may contain in the fluid sample is not particularly limited, and can be common
Various organic matters.Preferably, the fluid sample contains selected from ketone based compound (such as C3-C20Ketone), benzene compounds, alkane
Hydrocarbon (such as C1-C20Straight or branched alkane), halogenated hydrocarbons (such as C1-C20Halogenated hydrocarbons, halogen atom in the halogenated hydrocarbons can be with
It is chlorine atom, bromine atoms, fluorine atom or iodine atom) and aldehyde based compound (such as C1-C20Aldehyde) in one or more organic matter.
According to the present invention, the method that the fluid sample is analyzed is included using near infrared spectroscopy：By liquid-like
Product are supported on microporous barrier, and when the fluid sample contains water, the water on removing microporous barrier；The microporous barrier that will be obtained is placed in
Near-infrared spectrum analysis are carried out in infrared spectrometer.
The microporous barrier includes matrix and grafting at least one grafted moiety on the matrix, and described matrix is poly-
Ethene, polypropylene or ethylene-propylene copolymer, the grafted moiety are selected from the group shown in Formulas I and the group shown in Formula II,
In Formulas I, R1It is C8-C20Straight or branched alkyl, for example：Can be dodecyl and its isomers, the tetradecane
Base and its isomers, cetyl and its isomers, octadecyl and its isomers or eicosyl and its isomers；
In Formula II, R2And R3Respectively hydrogen or C1-C20Straight or branched alkyl.The C1-C20Straight or branched
The instantiation of alkyl can be included but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group,
The tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, hexyl and its isomers, heptyl and its isomers, octyl group and its isomery
Body, decyl and its isomers, dodecyl and its isomers, myristyl and its isomers, cetyl and its isomers, ten
Eight alkyl and its isomers or eicosyl and its isomers.
Preferably, in Formula II, R2And R3Respectively hydrogen or C8-C20Straight or branched alkyl；It is highly preferred that R2For
Hydrogen, R3It is C8-C20Straight or branched alkyl；It is further preferred that R2It is hydrogen, R3It is C8-C12Straight or branched alkyl.
The microporous barrier can pass through conventional various film build method systems by conventional method using previously described material
It is standby to obtain, it is also possible to be commercially available.
Specifically, the grafted moiety can be connected on matrix using various methods commonly used in the art.For example may be used
With by using radiation exposure described matrix, free radical is formed on the matrix as activated centre, and make acrylic acid with it is described
On matrix activated centre contact, with by radical reaction by acrylic acid-grafted onto described matrix, then by after grafting
Matrix and R1OH and/orContact, to carry out esterification and/or amidation process, so as to obtain Formulas I and/or formula
Grafted moiety shown in II.
The present invention to being not particularly limited for the species for irradiating described matrix to produce the ray in activated centre, Ke Yiwei
The various polymer chains that can make polyethylene, polypropylene or ethylene-propylene copolymer commonly used in the art produce penetrating for free radical
Line, for example：Alpha ray, β rays, gamma-rays, x-ray or electron beam, preferably gamma-rays.With radiation exposure described matrix when
Between appropriate selection can be carried out according to the content of the grafted moiety on expected matrix, to be able to ensure that the matrix for finally giving
On the content of grafted moiety disclosure satisfy that requirement is defined.Usually, the time of irradiation can be 1 minute to 1 hour, preferably
5 minutes to 30 minutes.
Can under normal conditions by the substrate contact at acrylic acid and active center, so that by acrylic acid-grafted to institute
State on matrix.Usually, acrylic molecules knot can be made at 40-80 DEG C by acrylic acid and the active substrate contact
C=C in structure is reacted with the activated centre in described matrix, so that by acrylic acid-grafted in described matrix.
The present invention is not particularly limited for the condition of the esterification and amidation process, can be commonly used in the art
Under conditions of carry out, as long as the content of the grafted moiety being able to ensure that in the microporous barrier for finally giving shown in Formulas I and Formula II can
Meet actual requirement.Preferably, the esterification and the amidation process are in the presence of at least one dehydrating agent
Carry out.It is highly preferred that the esterification and the amidation process enter in the presence of N, N '-dicyclohexylcarbodiimide
OK, the extent of reaction of esterification and amidation process so can further be improved.
The content of the grafted moiety in the microporous barrier can carry out appropriate selection according to specific requirement.Usually, with
On the basis of the total amount of the microporous barrier, the content of described matrix can be 65-99 weight %, and the content of the grafted moiety can be with
It is 1-35 weight %.Preferably, on the basis of the total amount of the microporous barrier, the content of described matrix can be 70-90 weight %,
Such as 75-85 weight %, the content of the grafted moiety can be 10-30 weight %, such as 15-25 weight %.
The present invention is not particularly limited for the average pore size and porosity in the hole in the microporous barrier, can be common
Aperture and porosity that microporous barrier with filtering function has.
The fluid sample can be supported on the microporous barrier using various methods commonly used in the art.For example：Can
Contacted with the microporous barrier with by the fluid sample, the organic matter in sample is adsorbed on microporous barrier.Specifically, can be with
Fluid sample is set to flow through the microporous barrier, during the fluid sample flows through the microporous barrier, in the fluid sample
Organic matter be adsorbed on microporous barrier；Fluid sample can also be added drop-wise to the microporous barrier, in making the fluid sample
Organic matter is adsorbed on microporous barrier.
The amount of fluid sample of the present invention for being contacted with the microporous barrier is not particularly limited, so that what is finally given is micro-
The amount of the organic matter on pore membrane disclosure satisfy that the requirement of specific tester is defined.
When the fluid sample also contains water, the method according to the invention is also loaded with the fluid sample including removing
Microporous barrier on water.Removing be loaded with water on the microporous barrier of the fluid sample condition can according to the content of water and
The species of the organic matter carries out appropriate selection.Usually, can remove and be loaded with the liquid at a temperature of 25-40 DEG C
Water on the microporous barrier of body sample.From the angle of the time for further shortening dehydration, preferably with least one nonactive gas
Body is purged to the microporous barrier for being loaded with the fluid sample.The non-active gas refer to not with water, the organic matter with
Can be various non-active gas commonly used in the art, for example and microporous barrier occurs chemically interactive gas：The non-live
Property gas can be selected from nitrogen and group 0 element gas (such as argon gas).
When being analyzed to the fluid sample using near infrared spectroscopy, can be by setting up class model and and class model
It is compared to differentiate whether the fluid sample contains organic matter, and is being determined as when containing organic matter, determines the type of organic matter.
Class model can be set up using conventional various methods.
Specifically, following step can be included in the method being analyzed to the fluid sample using near infrared spectroscopy
Suddenly：
(I-1) different type organic matter standard items are carried out into near-infrared spectrum analysis, obtains atlas of near infrared spectra and to having
Machine thing standard items are clustered；
(I-2) fluid sample is carried out into near-infrared spectrum analysis；
(I-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (I-1) determination, and containing step
(I-1) during the organic matter of the cluster for determining, the type of the organic matter is determined.
In step (I-2), infrared spectrum analysis is carried out to fluid sample using previously described method.
In step (I-1), when carrying out near-infrared spectrum analysis to organic matter standard items, can be using conventional sample preparation side
Method, that is, standard items are configured to solution and are analyzed in sample cell；Previously described method can also be used, will
Organic matter standard items are supported on microporous barrier, and the microporous barrier is placed in carries out near-infrared spectrum analysis in infrared spectrometer.
In the present invention, the cluster is that unknown data is assigned into inhomogeneous process by similarity degree, can be by conventional
Various clustering algorithms realize.
It is of the invention it is a kind of preferred embodiment in, in step (I-1), using principal component analysis-mahalanobis distance method
Organic matter standard items are clustered.
The method for using principal component analysis-mahalanobis distance method to cluster organic matter standard items can be conventional method.
Specifically, the atlas of near infrared spectra of standard items is converted into first derivative figure, by by the peak under different wave numbers in first derivative figure
Corresponding absorbance AsmThe matrix of formation carries out principal component analysis, determines the score of the principal component of each standard items, by it is described it is main into
The score divided calculates the mahalanobis distance at center of each standard items away from the class belonging to the standard items respectively, according to the mahalanobis distance pair
Standard items are clustered, and the center is the average value of the principal component scores of all standard items of the type.
Preferably, in step (I-1), extraction is scored at two principal components of front two and by the score of the two principal components
Mahalanobis distance of each standard items away from all kinds of centers is calculated respectively so as to be clustered to organic matter standard items.
It is highly preferred that in step (I-1), extraction is scored at the principal component of front two, makes this two loads of composition
Figure, and according to mahalanobis distance by load diagram subregion.So when differentiating whether sample contains organic matter and determine the species of organic matter,
Can intuitively differentiate whether sample contains organic matter and determine the species of organic matter by observing which subregion sample falls into.
From the angle for further improving precision of analysis, further preferably with the mahalanobis distance≤3.5 pair load diagram
Carry out subregion.
Correspondingly, in step (I-3), can differentiate whether the sample contains category using principal component analysis-mahalanobis distance method
The organic matter of the cluster determined in step (I-1), and in the organic matter of the cluster determined containing step (I-1), it is determined that this has
The type of machine thing.When step (I-3) will be scored at the load diagram subregion of two principal components of front two, in step (I-3), root
Differentiate whether the sample contains the organic matter of the subregion for falling with step (I-1) determination and determine the class of the organic matter according to mahalanobis distance
Type.
Specifically, the atlas of near infrared spectra of the fluid sample that can be obtained step (I-2) is converted into first derivative figure, root
According to the corresponding absorbance A in peak under the different wave numbers in the first derivative figure of samplemCarry out principal component analysis and determine principal component
Score, calculates the mahalanobis distance at all kinds of center that principal component is obtained to step (I-1), is sentenced according to the mahalanobis distance being calculated
Whether the not sample determines to be somebody's turn to do containing the organic matter for falling with the cluster (or subregion) that step (I-1) determines in when containing organic matter
The type of organic matter.
Different type organic matter standard items are clustered by principal component analysis-mahalanobis distance diagnostic method and is differentiated liquid
Whether body sample the organic matter containing the cluster (or subregion) for falling with step (I-1) determination and determines that the type of the organic matter can be with
Carried out on conventional various softwares, such as SPSS (Statistical Product and Service Solution, statistics
Product and service solution) software kit and matlab (Matrix Laboratory, matrix labotstory) software kit.
The method according to the invention, in step (I-1), can be according to organic matter that may be present in sample to be analyzed
Type determines the species of organic matter standard items and selects specific organic matter standard items.
For example, may be containing selected from ketone based compound (such as C in sample to be analyzed3-C20Ketone), benzene compounds, alkane
Hydrocarbon (such as C1-C20Straight or branched alkane), halogenated hydrocarbons (such as C1-C20Halogenated hydrocarbons, halogen atom in the halogenated hydrocarbons can be with
It is chlorine atom, bromine atoms, fluorine atom or iodine atom) and aldehyde based compound (such as C1-C20Aldehyde) in one or more organic matter
When, the type of the organic matter standard items causes that the cluster (or subregion) that step (I-1) is obtained at least contains with lower class：As
The halogenated alkane of I classes (or I areas), as the organic matter with carbonyl in class ii (or ii area), as group iii (or
III areas) the organic matter with phenyl ring.Specifically, the organic matter standard items can be chloroform, 1,2-dichloroethene, third
Ketone, formaldehyde, acrylamide, toluene, ortho-xylene, aniline, phenol and styrene.
The method according to the invention, the infrared spectrometer can be it is commonly used in the art it is various types of can carry out it is near
The infrared spectrometer of infrared spectrum analysis, does not have any restriction.
The present invention to the method that fluid sample is analyzed using three-dimensional fluorescence spectrum method for being not particularly limited.Typically
Whether ground, by setting up class model and being compared to contain organic matter in differentiation fluid sample with class model, and can sentence
It is not when containing organic matter, determines the type of organic matter.Class model can be set up using conventional various methods, and according to such
Whether model carries out containing organic matter in differentiation fluid sample, and is being determined as when containing organic matter, determines the type of organic matter.
Specifically, the method that fluid sample is analyzed is comprised the following steps using three-dimensional fluorescence spectrum method：
(II-1) different type organic matter standard items are carried out into three-dimensional fluorescence spectrum analysis, obtains three-dimensional fluorescence spectrum figure simultaneously
Organic matter standard items are clustered；
(II-2) fluid sample is carried out into three-dimensional fluorescence spectrum analysis；
(II-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (II-1) determination, and containing step
(II-1) during the organic matter of the cluster for determining, the type of the organic matter is determined.
In step (II-1), the cluster can be realized by the various clustering algorithms commonly used.
It is of the invention it is a kind of preferred embodiment in, in step (II-1), using principal component analysis-mahalanobis distance method
Organic matter standard items are clustered；In step (II-3), differentiate whether the sample contains according to mahalanobis distance method and belong to step
(II-1) organic matter of the cluster for determining, and in the organic matter of the cluster determined containing step (II-1), determine the organic matter
Type.
Specifically, fluorescence area can be divided into five subregions, the corresponding excitation wavelength of each subregion and launch wavelength exist
Listed in table 1 below.
Table 1
According to the excitation wavelength lambdaex sm, emission wavelength lambdaem smWith fluorescence intensity FIsmCalculate and be in five subregions listed by table 1
In fluorescence peak volume account in fluorescence area (that is, in five fluorescence areas) fluorescence peak cumulative volume percentage, calculate public
Formula is as follows：
Pi,n=Φi,n/ΦT,n× 100% (formula III)
In Formulas I, Formula II and formula III, ΦT,nIt is the cumulative volume of the fluorescence peak in fluorescence area；
Φi,nIt is the volume of the fluorescence peak in each fluorescence subregion；
Pi,nThe percentage of the cumulative volume of the fluorescence peak accounted in fluorescence area for the volume of the fluorescence peak in each fluorescence subregion；
I is fluorescence subregion, is 1,2,3,4 or 5；
ΔλexIt is the step-length (being 5nm) of excitation wavelength；
ΔλemIt is the step-length (being 5nm) of launch wavelength；
I(λex,λem) it is each corresponding fluorescence intensity of excitation-emission wavelength.
By 5 P of subregioni,nComposition one column vector carry out principal component analysis, determine each standard items principal component
Point, as the score of the principal component calculate respectively each standard items away from the standard items belonging to class center mahalanobis distance, according to
The mahalanobis distance is clustered to standard items, and the center is the average value of the principal component scores of all standard items of the type.
Preferably, step (II-1) extraction is scored at two principal components of front two and by the score point of the two principal components
Mahalanobis distance of each standard items away from all kinds of centers is not calculated so as to be clustered to organic matter standard items.
It is highly preferred that in step (II-1), extraction is scored at the principal component of front two, makes this two loads of composition
Figure, and according to mahalanobis distance by load diagram subregion.So differentiating whether sample containing organic matter and determines the species of organic matter
When, can intuitively differentiate whether sample contains organic matter and determine the kind of organic matter by observing which subregion sample falls into
Class.From the angle for further improving precision of analysis, further preferably with the mahalanobis distance≤4 pair load diagram
Carry out subregion.
In step (II-3), 5 P of subregion of the three-dimensional fluorescence spectrum figure of the sample that calculation procedure (II-2) is obtainedi,n,
And 5 P of subregion that will be obtainedi,nThe score that principal component analysis determines principal component is carried out, principal component to step (II-1) is calculated and is obtained
The mahalanobis distance at all kinds of center arrived, differentiates whether the sample contains and falls with step (II- according to the mahalanobis distance being calculated
1) organic matter of the cluster for determining and the type of the organic matter is determined.Step (II-1) will be scored at two of front two it is main into
During the load diagram subregion for dividing, in step (II-3), differentiate whether the sample is true containing step (II-1) is fallen with according to mahalanobis distance
The organic matter of fixed subregion simultaneously determines the type of the organic matter.
Different type organic matter standard items are clustered by principal component analysis-mahalanobis distance diagnostic method and is differentiated institute
State whether fluid sample the organic matter containing the cluster for belonging to step (II-1) determination and determines that the type of the organic matter can be
Carried out on conventional various softwares, such as SPSS software kits and matlab software kits.
Three-dimensional fluorescence spectrum analysis can be carried out to organic matter standard items and the fluid sample using conventional method, do not had
It is particularly limited to.
In step (II-1), organic matter can be determined according to the type of organic matter that may be present in sample to be analyzed
The species of standard items simultaneously selects specific organic matter standard items.
For example, may be containing selected from ketone based compound (such as C in sample to be analyzed3-C20Ketone), benzene compounds, alkane
Hydrocarbon (such as C1-C20Straight or branched alkane), halogenated hydrocarbons (such as C1-C20Halogenated hydrocarbons, halogen atom in the halogenated hydrocarbons can be with
It is chlorine atom, bromine atoms, fluorine atom or iodine atom) and aldehyde based compound (such as C1-C20Aldehyde) in one or more organic matter
When, the type of organic matter standard items described in step (II-1) causes that the cluster (or subregion) that step (II-1) is obtained at least is wrapped
Include：What the compound and nitrogen-atoms for containing nitrogen-atoms as the substitution base on the phenyl ring in I classes (or I areas) were bonded with phenyl has
Machine thing, the organic matter of halogen atom is contained as the substitution base on the phenyl ring in class ii (or ii area), as group iii (or
Ii I areas) phenyl ring on substitution base containing only carbon, three kinds of organic matters of atom of hydrogen and oxygen, as iv class (or iv area)
Organic matter without phenyl ring.Specifically, the organic matter standard items can for aniline, 4- nitros phenyl ethylamine, benzidine, to dichloro
Benzene, pentachlorophenol, 2,4,5-D (alternatively referred to as drip 245 or D245 or 245D, i.e.), acetone,
1,2- dichloroethylene, toluene, phenol, ethylbenzene, ortho-xylene, mellitene and ethyl benzoate.
From the angle of the accuracy for further improving examination, the method for the present invention can also include using ultraviolet spectroscopy
The fluid sample is analyzed.
Specifically, the method that the fluid sample is analyzed is included using ultraviolet spectroscopy：
(III-1) different type organic matter standard items are carried out into ultraviolet full scan, obtains ultraviolet spectrogram and to organic
Thing standard items are clustered；
(III-2) fluid sample is carried out into ultraviolet full scan, obtains ultraviolet spectrogram；
(III-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (III-1) determination, and containing step
Suddenly during the organic matter of the cluster that (III-1) determines, the type of the organic matter is determined.
In step (III-1), the cluster can be realized by the various clustering algorithms commonly used.It is excellent in one kind of the invention
In the implementation method of choosing, in step (III-1), organic matter standard items are clustered using principal component analysis-mahalanobis distance method；
In step (III-3), differentiate whether the sample contains using principal component analysis-mahalanobis distance method and belong to step (III-1) determination
Cluster organic matter, and in the organic matter of the cluster determined containing step (III-1), determine the type of the organic matter.
The method for using principal component analysis-mahalanobis distance method to cluster organic matter standard items can be conventional method.
Specifically, in step (III-1), the matrix that will be formed by the corresponding absorbance of absworption peak under different wave length in ultraviolet spectrogram
Principal component analysis is carried out, the score of the principal component of each standard items is determined, each standard items are calculated by the score of the principal component respectively
Standard items are clustered by the mahalanobis distance at the center away from the class belonging to the standard items according to the mahalanobis distance, the center
It is the average value of the principal component scores of all standard items of the type.
Preferably, in step (III-1), extraction is scored at two principal components of front two and obtaining by the two principal components
Divide and calculate mahalanobis distance of each standard items away from all kinds of centers respectively so as to be clustered to organic matter standard items.
It is highly preferred that in step (III-1), extraction is scored at the principal component of front two, makes this two lotuses of composition
Figure is carried, and according to mahalanobis distance by load diagram subregion.So differentiating whether sample containing organic matter and determines the kind of organic matter
During class, can intuitively differentiate whether sample contains organic matter and determine organic matter by observing which subregion sample falls into
Species.From the angle for further improving precision of analysis, further preferably with the mahalanobis distance≤7.5 pair lotus
Load figure carries out subregion.
In step (III-3), differentiate whether the sample contains according to mahalanobis distance method and fall with the poly- of step (III-1) determination
The organic matter of class, and in the organic matter of the cluster determined containing step (III-1), determine the type of the organic matter.In step
(III-1) when will be scored at the load diagram subregion of two principal components of front two, in step (III-3), sentenced according to mahalanobis distance
Whether the sample does not contain the organic matter of the subregion for belonging to step (III-1) determination and determines the type of the organic matter.
Specifically, in step (III-3), in the ultraviolet spectrogram that step (III-2) can be obtained under different wave length
The corresponding absorbance of absworption peak carries out the score that principal component analysis determines principal component, calculates principal component to step (III-1) and obtains
All kinds of centers mahalanobis distance, differentiate the sample whether containing falling with step (III- according to the mahalanobis distance being calculated
1) organic matter of the cluster (or subregion) for determining and the type of the organic matter is determined.
Different type organic matter standard items are clustered by principal component analysis-mahalanobis distance diagnostic method and is differentiated institute
State the class whether fluid sample contains the organic matter of the cluster (or subregion) for falling with step (III-1) determination and determine the organic matter
Type can be carried out on conventional various softwares, such as SPSS software kits and matlab software kits.
The method according to the invention, in step (III-1), can be according to organic matter that may be present in sample to be analyzed
Type determine the species of organic matter standard items and select specific organic matter standard items.
For example, may be containing selected from ketone based compound (such as C in sample to be analyzed3-C20Ketone), benzene compounds, alkane
Hydrocarbon (such as C1-C20Straight or branched alkane), halogenated hydrocarbons (such as C1-C20Halogenated hydrocarbons, halogen atom in the halogenated hydrocarbons can be with
It is chlorine atom, bromine atoms, fluorine atom or iodine atom) and aldehyde based compound (such as C1-C20Aldehyde) in one or more organic matter
When, the type of the organic matter standard items causes that the cluster (or subregion) that step (III-1) is obtained at least includes：As I classes
The organic matter without phenyl ring in (or I areas), as the organic matter containing phenyl ring or heterocycle of class ii (or ii area), as
The polycyclic aromatic hydrocarbon of Group III (or ii I areas).Specifically, the organic matter standard items can be chloroform, trichloro ethylene, first
Alcohol, formaldehyde, ether, phenol, styrene, paracide, ethyl benzoate, aniline, pentachlorophenol, 2,4,6- trichlorophenol, 2,4,6,-Ts, 2,4,
5-D, prometryn are (i.e.,), benzidine, 1,3- dinitrotoluene (DNT)s, 4- nitros phenyl ethylamine, pentanone,
Anthracene and phenanthrene.
The present invention is for organic matter standard items and the fluid sample to be carried out the method for ultraviolet spectral analysis without special
Limit, can under normal conditions be carried out on conventional ultraviolet spectrometer.
The method according to the invention is particularly well-suited to carry out the organic matter in sewage the occasion of rapid screening.Specifically,
The fluid sample can be to come from the sewage of chemical industry, come from the sewage of petroleum industry or come from the dirt of hospital
Water.
The present invention is described in detail below in conjunction with test case and embodiment.
In following test case, test comparison example, embodiment and comparative example, the infrared spectrometer for using is commercially available from Thermo
The model Antaris II of Scientific TruProcess are simultaneously equipped with by the Fourier transform-red of near-infrared fibre-optical annex
External spectrum instrument, its resolution ratio is 8cm-1, sweep limits is 4000-10000cm-1, scanning times are 64 times, using absorption mode.
In following test case, test comparison example, embodiment and comparative example, Hitachi F-7000 types fluorescence spectrophotometer point is used
Degree meter carries out three-dimensional fluorescence spectrum analysis, wherein, sweep limits is excitation wavelength=200-600nm, launch wavelength=200-
600nm, sweep speed is 1200nm/min, and test sample is fitted into the quartzy fluorescent samples pond of 1cm.
In following test case, test comparison example, embodiment and comparative example, the S52 uv-spectrophotometrics purchased from HACH are used
Meter carries out ultraviolet spectral analysis, wherein, sweep limits is 200-700nm, at intervals of 1nm, using the quartz colorimetric utensil of 1cm.
In following examples, principal component analysis and geneva are carried out using SPSS20.0 software kits and the software kits of matlab 7.0
Distance is calculated.
Test case 1-2 is used to illustrate the near infrared spectroscopy in the method for the present invention.
Test case 1
(1) aqueous acetone solution that 0.2 milligram of concentration is 49.6 weight % is added drop-wise on microporous barrier (commercially available from Tianjin Beaune
Jie Er Science and Technology Ltd.s, matrix is polyethylene, and grafted moiety isGrafted moiety
Content be 16 weight %, the content of matrix is 84 weight %)；Then microporous barrier is purged 30 in room temperature (being 25 DEG C) with nitrogen
Minute, so as to obtain the sample for near-infrared spectrum analysis.
(2) being placed in sample prepared by step (1) carries out near-infrared spectrum analysis in infrared spectrometer.The near-infrared for obtaining
Spectrogram is as shown in Figure 1.
(3) spectrogram that step (2) is obtained is converted into first derivative spectrum figure, as shown in Figure 2.
Test comparison example 1
(1) will be equipped with the sample cell (sample cell specification is 0.2cm × 1cm × 3cm) of the acetone that concentration is 99.2 weight %
It is placed in infrared spectrometer, carries out near-infrared spectrum analysis, the atlas of near infrared spectra for obtaining is as shown in Figure 3.
(2) spectrogram that step (1) is obtained is converted into first derivative spectrum figure, as shown in Figure 4.
Test comparison example 2
(1) sample cell (specification is with comparative example 1) that will be equipped with the acetone that concentration is 49.6 weight % is placed in infrared spectrometer
In, near-infrared spectrum analysis are carried out, the atlas of near infrared spectra for obtaining is as shown in Figure 5.
(2) spectrogram that step (1) is obtained is converted into first derivative spectrum figure, as shown in Figure 6.
Fig. 1 and Fig. 3 and Fig. 5 are compared, Fig. 2 and Fig. 4 and Fig. 6 are compared as can be seen that of the invention
Method can effectively eliminate the interference information in sample, can clearly be observed that acetone is located at 5660cm-1Characteristic absorption
Peak.
Test case 2
(1) it is 0.2 milligram of concentration is (outstanding commercially available from Tianjin Beaune for the aqueous solution of the toluene of 5mg/L is added drop-wise on microporous barrier
That Science and Technology Ltd., matrix is polypropylene, and grafted moiety isGrafted moiety
Content is 25 weight %, and the content of matrix is 75 weight %)；Then microporous barrier is purged 30 points in room temperature (being 25 DEG C) with nitrogen
Clock, so as to obtain the sample for near-infrared spectrum analysis.
(2) being placed in sample prepared by step (1) carries out near-infrared spectrum analysis in infrared spectrometer.The spectrogram for obtaining is such as
Shown in Fig. 7.
(3) spectrogram that step (2) is obtained is converted into first derivative spectrum figure, as shown in Figure 8.
Can clearly be observed that toluene is located at 5760cm from Fig. 7 and Fig. 8-1Characteristic absorption peak.
The result of test case 1-2 shows that the inventive method is supported on microporous barrier by by liquid, aqueous sample, and is removed
Water on microporous barrier, can effectively deduct the interference information that the water in sample is produced such that it is able to improve liquid, aqueous sample
Near-infrared spectrum analysis validity and accuracy, it is adaptable to various aqueous organic matters are analyzed.
Embodiment 1
The present embodiment is used to illustrate the method for the present invention.
I, near-infrared spectrum analysis
(I-1) standard items are attached separately in infrared spectrometer sample cell, carry out near-infrared spectrum analysis, obtain near red
External spectrum figure, the atlas of near infrared spectra conversion product first derivative spectrum figure that will be obtained.Standard items include：Chloroform, 1,2- bis-
Vinyl chloride, acetone, formaldehyde, acrylamide, toluene, ortho-xylene, aniline, phenol and styrene.
The matrix formed by the absorbance in the 108 of first derivative spectrum figure wave numbers is carried out with SPSS20.0 software kits
Principal component analysis, determines the score of the principal component of each standard items.Extraction is scored at two principal components of front two and by the two
The score of principal component, mahalanobis distance of each standard items away from all kinds of centers is calculated with the software kits of matlab 7.0 respectively, so that
Organic matter standard items are clustered, determines all kinds of borders (that is, to being scored at the two of front two with mahalanobis distance≤3.5
The load diagram of individual composition carries out subregion).Obtain being scored at load diagram and division result such as Fig. 9 institutes of the principal component of front two
Show.
From fig. 9, it can be seen that the load diagram for being scored at two principal components of front two is divided into three areas.Wherein, I areas
It is halogenated alkane；Ii area is the organic matter with carbonyl；Ii I areas are the organic matter with phenyl ring.
(I-2) by concentration for the D24 of 1mg/L (also referred to as drips 24, i.e.,) water-soluble drop
It is added on microporous barrier (identical with test case 1)；Then microporous barrier is purged 30 minutes in room temperature (being 25 DEG C) with nitrogen, so that
To the sample for near-infrared spectrum analysis.
The sample of preparation is placed in carries out near-infrared spectrum analysis in infrared spectrometer, the spectrogram for obtaining is as shown in Figure 10.
The atlas of near infrared spectra for obtaining is converted into first derivative spectrum figure, as shown in figure 11.
(I-3) the absorbance SPSS software kits in 108 wave numbers of the first derivative spectrum figure for obtaining step (I-2)
Carry out principal component analysis and calculate mahalanobis distance with the software kits of matlab 7.0, as a result as shown in figure 12.It is possible thereby to judge this
Sample contains group iii organic matter.
II, three-dimensional fluorescence spectrum analysis
(II-1) standard items are attached separately in sample cell, carry out three-dimensional fluorescence spectrum analysis.Standard items include：4- nitros
Phenyl ethylamine, benzidine, paracide, pentachlorophenol, drop 245, acetone, 1,2- dichloroethylene, toluene, phenol, ethylbenzene, adjacent diformazan
Benzene, mellitene and ethyl benzoate.
The volume for calculating the fluorescence peak in five subregions listed by table 1 accounts in fluorescence area (that is, five fluorescence areas
It is interior) percentage of the cumulative volume of fluorescence peak, computing formula is as follows：
Pi,n=Φi,n/ΦT,n× 100% (formula III)
In Formulas I, Formula II and formula III, ΦT,nIt is the cumulative volume of the fluorescence peak in fluorescence area；
Φi,nIt is the volume of the fluorescence peak in each fluorescence subregion；
Pi,nThe percentage of the cumulative volume of the fluorescence peak accounted in fluorescence area for the volume of the fluorescence peak in each fluorescence subregion；
I is fluorescence subregion, is 1,2,3,4 or 5；
ΔλexIt is the step-length (being 5nm) of excitation wavelength；
ΔλemIt is the step-length (being 5nm) of launch wavelength；
I(λex,λem) it is each corresponding fluorescence intensity of excitation-emission wavelength.
With SPSS20.0 software kits by 5 P of subregioni,nOne column vector of composition carries out principal component analysis, determines each standard
The score of the principal component of product, each standard items are calculated away from the mark using the software kits of matlab 7.0 respectively by the score of the principal component
Standard items are clustered by the mahalanobis distance at the center of the class belonging to quasi- product according to the mahalanobis distance, and the center is such
The average value of the principal component scores of all standard items of type.Wherein, extract and be scored at two principal components of front two and by the two
The score of principal component, mahalanobis distance of each standard items away from all kinds of centers is calculated so as to right with the software kits of matlab 7.0 respectively
Organic matter standard items are clustered；Determined with mahalanobis distance≤4 all kinds of border (that is, to be scored at two of front two into
The load diagram for dividing carries out subregion).The load diagram and division result for obtaining being scored at the principal component of front two are as shown in figure 13.
As can be seen from Figure 13, the load diagram for being scored at two principal components of front two is divided into four areas.Wherein, I
Area is the organic matter that the compound and nitrogen-atoms that the substitution base on phenyl ring contains nitrogen-atoms are bonded with phenyl；Ii area is on phenyl ring
Substitution base contain the organic matter of halogen atom；Ii I areas are substitution base the having containing only carbon, hydrogen and three kinds of atoms of oxygen on phenyl ring
Machine thing；Organic matter of the iv area without phenyl ring.
(II-2) concentration is carried out into three-dimensional fluorescence spectrum analysis for the D24 aqueous solution of 1mg/L is placed in sample cell, three are obtained
Dimension fluorescence spectra is as shown in figure 14.
(II-3) the three-dimensional fluorescence spectrum figure for obtaining step (II-2) is carried out using the method similar to step (II-1)
Principal component analysis simultaneously calculates mahalanobis distance, as a result as shown in figure 15, it is possible thereby to judge that the sample contains ii type organic.
III, ultraviolet spectral analysis
(III-1) standard items are attached separately in sample cell, carry out ultraviolet spectral analysis, the full scan spectrogram for obtaining.Mark
Quasi- product include：Chloroform, trichloro ethylene, methyl alcohol, formaldehyde, ether, phenol, styrene, paracide, ethyl benzoate, benzene
Amine, pentachlorophenol, 2,4,6- trichlorophenol, 2,4,6,-Ts, 2,4,5-D, prometryn, benzidine, 1,3- dinitrotoluene (DNT)s, 4- nitros phenyl ethylamine, penta
Ketone, anthracene and phenanthrene.
The matrix that will be formed by the absorbance of full scan spectrogram with SPSS20.0 software kits carries out principal component analysis, it is determined that respectively
The score of the principal component of standard items.Extraction is scored at two principal components of front two and by the score of the two principal components, uses
The software kits of matlab 7.0 calculate mahalanobis distance of each standard items away from all kinds of centers so as to enter to organic matter standard items respectively
Row cluster, determines that all kinds of borders (that is, are entered to the load diagram for being scored at two compositions of front two with mahalanobis distance≤7.5
Row subregion).The load diagram and division result for obtaining being scored at the principal component of front two are as shown in figure 16.
As can be seen from Figure 16, the load diagram for being scored at two principal components of front two is divided into three areas.Wherein, I
Area is the organic matter without phenyl ring；Ii area is the organic matter containing phenyl ring or heterocycle；Ii I areas are polycyclic aromatic hydrocarbon.
(III-2) concentration is obtained into ultraviolet spectrogram (such as Figure 17 institutes for the D24 aqueous solution of 1mg/L carries out ultraviolet full scan
Show).
(III-3) ultraviolet spectrogram that step (III-2) is obtained is carried out into principal component analysis and calculates mahalanobis distance, as a result
As shown in figure 18.It is possible thereby to judge the organic matter that the sample contains class ii.
Embodiment 1 as a result, it was confirmed that the method for the present invention can be realized accurately entering the organic matter in fluid sample
Row examination.
Claims (10)
1. a kind of method that organic matter in fluid sample carries out examination, the method includes three-dimensional fluorescence spectrum method is respectively adopted
Fluid sample is analyzed near infrared spectroscopy, whether to differentiate the fluid sample containing organic matter, and in when containing organic matter
Determine the species of the organic matter,
Wherein, the method that fluid sample is analyzed is included using near infrared spectroscopy：Fluid sample is supported on microporous barrier
On, and when the fluid sample contains water, the water on removing microporous barrier；The microporous barrier that will be obtained is placed in infrared spectrometer
Row near-infrared spectrum analysis,
The microporous barrier includes matrix and grafting at least one grafted moiety on the matrix, and described matrix is poly- second
Alkene, polypropylene or ethylene-propylene copolymer, the grafted moiety are selected from the group shown in Formulas I and the group shown in Formula II,
In Formulas I, R1It is C8-C20Straight or branched alkyl；
In Formula II, R2And R3Respectively hydrogen or C1-C20Straight or branched alkyl.
2. method according to claim 1, wherein, the side being analyzed to the fluid sample using near infrared spectroscopy
Method is comprised the following steps：
(I-1) different type organic matter standard items are carried out into near-infrared spectrum analysis, obtains atlas of near infrared spectra and to organic matter
Standard items are clustered；
(I-2) fluid sample is carried out into near-infrared spectrum analysis；
(I-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (I-1) determination, and containing step (I-1)
During the organic matter of the cluster of determination, the type of the organic matter is determined.
3. method according to claim 1, wherein, on the basis of the total amount of the microporous barrier, the content of described matrix is
65-99 weight %, the content of the grafted moiety is 1-35 weight %.
4. method according to claim 1, wherein, the fluid sample is analyzed using three-dimensional fluorescence spectrum method
Method is comprised the following steps：
(II-1) different type organic matter standard items are carried out into three-dimensional fluorescence spectrum analysis, obtains three-dimensional fluorescence spectrum figure and to having
Machine thing standard items are clustered；
(II-2) fluid sample is carried out into three-dimensional fluorescence spectrum analysis；
(II-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (II-1) determination, and containing step (II-
1) during the organic matter of the cluster for determining, the type of the organic matter is determined.
5. method according to claim 1, wherein, the method also includes entering the fluid sample using ultraviolet spectroscopy
Row analysis.
6. method according to claim 5, wherein, the method being analyzed to the fluid sample using ultraviolet spectroscopy
Including：
(III-1) different type organic matter standard items are carried out into ultraviolet full scan, obtains ultraviolet spectrogram and to organic matter mark
Quasi- product are clustered；
(III-2) fluid sample is carried out into ultraviolet full scan, obtains ultraviolet spectrogram；
(III-3) differentiate whether the sample contains the organic matter of the cluster for belonging to step (III-1) determination, and containing step
(III-1) during the organic matter of the cluster for determining, the type of the organic matter is determined.
7. the method according to any one in claim 2,5 and 6, wherein, in step (I-1), using principal component analysis-
Mahalanobis distance method is clustered to organic matter standard items, and in step (I-3), being differentiated using principal component analysis-mahalanobis distance method should
Whether sample contains the organic matter of the cluster for belonging to step (I-1) determination, and in the organic of the cluster determined containing step (I-1)
During thing, the type of the organic matter is determined；
In step (II-1), organic matter standard items are clustered using principal component analysis-mahalanobis distance method, step (II-3)
In, differentiate whether the sample contains the organic of the cluster for belonging to step (II-1) determination using principal component analysis-mahalanobis distance method
Thing, and in the organic matter of the cluster determined containing step (II-1), determine the type of the organic matter；
In step (III-1), organic matter standard items are clustered using principal component analysis-mahalanobis distance method, step (III-3)
In, differentiate whether the sample contains the organic of the cluster for belonging to step (III-1) determination using principal component analysis-mahalanobis distance method
Thing, and in the organic matter of the cluster determined containing step (III-1), determine the type of the organic matter.
8. method according to claim 7, wherein, in step (I-1), extraction is scored at two principal components of front two,
The load diagram of the two principal components is made, subregion is carried out with the mahalanobis distance≤3.5 pair load diagram, in step (I-3), according to
Mahalanobis distance differentiates whether the sample contains the organic matter of the subregion for falling with step (I-1) determination and determine the class of the organic matter
Type；
In step (II-1), extraction is scored at two principal components of front two, the load diagram of the two principal components is made, with geneva
≤ 4 pairs of load diagrams of distance carry out subregion, in step (II-3), differentiate whether the sample contains according to mahalanobis distance and fall with step
Suddenly the organic matter of the subregion that (II-1) determines and the type of the organic matter is determined；
In step (III-1), extraction is scored at two principal components of front two, the load diagram of the two principal components is made, with horse
Family name's≤7.5 pairs of load diagrams of distance carry out subregion, in step (III-3), differentiate whether the sample contains according to mahalanobis distance
Belong to the organic matter of the subregion of step (III-1) determination and determine the type of the organic matter.
9. method according to claim 8, wherein, the type of the organic matter standard items in step (I-1) causes step (I-
1) subregion for obtaining includes：As the halogenated alkane in I areas, as the organic matter with carbonyl in ii area, as ii I areas
Organic matter with phenyl ring；
The type of the organic matter standard items in step (II-1) causes that the subregion that step (II-1) is obtained includes：As I areas
The organic matter that the compound and nitrogen-atoms that substitution base on phenyl ring contains nitrogen-atoms are bonded with phenyl, on the phenyl ring as ii area
Substitution base contain the organic matter of halogen atom, as the substitution base on the phenyl ring in ii I areas containing only carbon, three kinds of atoms of hydrogen and oxygen
Organic matter, as the organic matter without phenyl ring in iv area；
The type of the organic matter standard items in step (III-1) causes that the subregion that step (III-1) is obtained includes：As I areas
The organic matter without phenyl ring, as the organic matter containing phenyl ring or heterocycle in ii area, as the polycyclic aromatic hydrocarbon in ii I areas.
10. the method according to any one in claim 1-6,8 and 9, wherein, the fluid sample contains selected from ketone system
One or more organic matter in compound, benzene compounds, alkane, halogenated hydrocarbons and aldehyde based compound.
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| CN1171412A (en) * | 1996-06-19 | 1998-01-28 | 希尔斯股份公司 | Hydrophilic coating surfaces of polymeric substrates |
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| CN1171412A (en) * | 1996-06-19 | 1998-01-28 | 希尔斯股份公司 | Hydrophilic coating surfaces of polymeric substrates |
| CN102512999A (en) * | 2006-04-11 | 2012-06-27 | 麻省理工学院 | Fouling resistant membranes formed with polyacrylonitrile graft copolymers |
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| Title |
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| 聚偏氟乙烯分离膜改性研究进展;王庐岩;《膜科学与技术》;20021031;第22卷(第5期);全文 * |
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