CN110160980A - Analysis method, analytical equipment and the Systems for optical inspection of sample absorbance change rate - Google Patents
Analysis method, analytical equipment and the Systems for optical inspection of sample absorbance change rate Download PDFInfo
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- CN110160980A CN110160980A CN201910554277.1A CN201910554277A CN110160980A CN 110160980 A CN110160980 A CN 110160980A CN 201910554277 A CN201910554277 A CN 201910554277A CN 110160980 A CN110160980 A CN 110160980A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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Abstract
The present invention relates to a kind of analysis methods of sample absorbance change rate, comprising: 1) is fitted to the time series data point in predetermined interval, obtains matched curve；2) the tentative starting point A and tentative terminal M of reaction phase are stablized in primary election, and point N is found on absorbance curve；3) final election starting point W is determinedstart, determine final election terminal Wend；4) final election starting point W is chosenstartWith final election terminal WendBetween time series data point analysis sample absorbance change rate.The analysis method can guarantee sample absorbance change rate precision of analysis and reliability.The invention also discloses a kind of analytical equipment of sample absorbance change rate and a kind of Systems for optical inspection.
Description
Technical field
The present invention relates to detection technique field, in particular to sample absorbance used in a kind of medical treatment or chemical field becomes
Rate analysis method, analytical equipment and Systems for optical inspection.
Background technique
By taking medical science as an example, turbidimetry is generallyd use to DD, FDP etc. in blood coagulation project and is detected.
The principle of turbidimetry are as follows: the transmitted light that light source and optical fiber generate is from one end directive transparent reaction cup, reaction cup
The other end received using photocell and transmitted light and be translated into signal value.When reaction persistently carries out, substance in reaction cup
Turbidity will increase, thus with the extension of reaction time, the intensity of transmitted light and the signal value after conversion will gradually reduce,
By the lasting detection of a period of time, the signal value curve of an available continuous decrease, according to Lambert-Beer
(Lambert-Beer) law:Absorbance curve, I in formula can be obtained by signal value curve0Represent into
Penetrate light intensity, ItThe output intensity of t moment is represented, A represents absorbance, and absorbance curve is usually using the time as abscissa, absorbance
For ordinate.
As shown in fig. 1, in the initial reaction phase S that test starts, belong to unstable reaction phase, the upper raising speed of absorbance
Rate is gradually increased, but its climbing speed and unstable；In stabilization reaction phase R later, belongs to the constant rate of speed reaction phase, inhale
Luminosity rises substantially according to a certain constant rate；In reaction was completed after this phase E, belong to deceleration reaction phase, absorbance
Climbing speed gradually slow down, different reaction samples, initial reaction phase S, to stablize reaction phase R and reaction was completed phase E logical
Difference often is had, the determination in above-mentioned each stage of differential responses sample at present is usually to pass through lot of experimental data to combine statistics
What rule was completed, it is known as experience starting point and experience according to the starting point and end point that count each reaction phase obtained and terminates
Point.
Performance rate method is a kind of common method calculated at present absorbance change rate, and performance rate method is calculating absorbance change
It is exactly aforementioned stable reaction phase R during selected reaction when rate, however, stablizing when the concentration of sample generates variation
The initial position of reaction phase R and end position actually also have corresponding change, and are adjusted in performance rate method not to this at present,
The initial position of stabilization reaction phase R and end position selected by the different same sample of concentration are consistent.Therefore pass through
Performance rate method the accuracy of calculated absorbance change rate need to be improved.
Summary of the invention
In order to solve the above-mentioned technical problem, first aspect present invention discloses a kind of analysis side of sample absorbance change rate
Method, so as to more accurately calculate the change rate of absorbance.
Second aspect of the present invention is to disclose a kind of analysis of absorbance change rate that can be realized above-mentioned analysis method
Device；
Third aspect present invention is to disclose a kind of optical detection system using above-mentioned absorbance change rate analysis method
System.
The analysis method of sample absorbance change rate disclosed in first aspect in the present invention, comprising:
1) the time series data point in predetermined interval is fitted, obtains absorbance curve；
2) primary election is stablized the tentative starting point A of reaction phase and is fixed tentatively eventually on the absorbance curve in the predetermined interval
Point M, and obtained on the absorbance curve between the tentative starting point A and the tentative terminal M and meet the first default item
The point N of part, first preset condition are as follows: the tangent slope of the excessively described point N is equal to the tentative starting point A and the tentative terminal
The line slope D of M1；
3) final election starting point W is determined between the tentative starting point A and the point Nstart；In the point N and the tentative end
Final election terminal W is determined between point Mend；
4) the final election starting point W is chosenstart
With the final election terminal WendBetween the time series data point analysis sample absorbance change rate.
Preferably, in the step 3), the final election starting point W is determinedstartMethod are as follows:
Between the tentative starting point A and the point N, meet the point P of the second preset condition if it exists, then it will be with the point
The nearest point P of N distance is recorded as final election starting point Wstart, second preset condition are as follows: the curvature k of the point PpMeet item
Part | kn-kp| > R, R are decision threshold, knFor the curvature of point N.
Preferably, in the step 3), the final election terminal W is determinedendMethod are as follows: the point N is recorded as described
Final election terminal Wend。
Preferably, in the step 3), the final election terminal W is determinedendMethod are as follows:
Between the point N and the tentative terminal M, meet the point q of third preset condition if it exists, then it will be with the point
The nearest point q of N distance is recorded as stablizing the final election terminal W of reaction phaseend, wherein the third preset condition are as follows: described
The curvature k of point qqMeet condition | kn-kq| > R, R are decision threshold, knFor the curvature of point N.
Preferably, in the step 3), meet the point P of second preset condition if it does not exist, then it will be described tentative
Starting point A is as final election starting point Wstart。
Preferably, in the step 3), meet the point q of third preset condition if it does not exist, then by the tentative terminal M
As the final election terminal Wend。
Preferably, in the step 2), the method for the tentative starting point A and tentative terminal M of primary election stable reaction phase are as follows:
Last collected time series data point B is chosen, according to sample type, chooses the experience starting point work for stablizing the reaction phase
Line slope for the tentative starting point A, the tentative starting point A and the time series data point B is D2, in the absorbance curve
On find tangent slope equal to D2Point, and using the point as the tentative terminal M.
Preferably, it between the step 3) and the step 4), further comprises the steps of:
31) in the final election starting point WstartWith the final election terminal WendBetween time domain span be less than fitminWhen, it forces
The mobile final election starting point WstartAnd/or the final election terminal Wend, make the final election starting point WstartWith the final election terminal Wend
Between time domain span reach fitmin, wherein fitminFor minimum time domain span.
Preferably, the mobile final election starting point W is forcedstartAnd/or the final election terminal WendMethod are as follows:
Obtain the final election starting point WstartThe time domain span L between the tentative starting point A1；Obtain the tentative end
The point M and final election terminal WendBetween time domain span L2If L1< L2, then positive to move the final election terminal Wend；If L1>
L2, then the final election starting point W is inversely movedstartIf L1=L2, then the final election starting point W is symmetrically movedstartIt is whole with the final election
Point Wend。
Preferably, the mobile final election starting point W is forcedstartAnd/or the final election terminal WendMethod are as follows:
Obtain the final election terminal WendWith the time domain span L between the tentative starting point A, if L >=fitmin, then reverse to move
Move the final election starting point Wstart；If L < fitmin, then the final election starting point W is inversely movedstartThe extremely tentative starting point A, and just
To the movement final election terminal Wend, so that the final election starting point WstartWith the final election terminal WendBetween time domain span reach
fitmin。
Preferably, in the step 4), to the final election starting point WstartWith the final election terminal WendBetween it is described when
Ordinal number strong point carries out linear fit, and the straight slope D after fitting is calculated0, according to the straight slope D0Sample is obtained to inhale
Light varience rate.
The analytical equipment of sample absorbance change rate disclosed in second aspect of the present invention, comprising:
Fitting module obtains absorbance curve for being fitted to the time series data point in predetermined interval；
Stablize and react initial modeling block, reaction is stablized in primary election on the absorbance curve in the predetermined interval
The tentative starting point A and tentative terminal M of phase；
First median point obtains module, for the absorbance between the tentative starting point A and the tentative terminal M
The point N for meeting the first preset condition, first preset condition are obtained on curve are as follows: the tangent slope of the excessively described point N is equal to institute
State the line slope D of tentative starting point A Yu the tentative terminal M1；
Final election starting point obtains module, for obtaining final election starting point W between the tentative starting point A and the point Nstart；
Final election terminal obtains module, for obtaining final election terminal W between the point N and the tentative terminal Mend；
Absorbance change rate analysis module, for choosing the final election starting point WstartWith the final election terminal WendBetween
The data point analysis sample absorbance change rate.
Preferably, further includes:
Second Intermediate Value point obtains module, for the tentative starting point A and last collected time series data point B it
Between the absorbance curve on obtain tangent slope be equal to D2Point, and the point is recorded as described in the tentative terminal M supplies
Primary election module uses, wherein D2For the line slope of the tentative starting point A and the time series data point B.
Preferably, further includes:
Comparison module is used for the stable region final election starting point WstartWith the stable region final election terminal WendBetween
Whether time domain span is less than fitmin, wherein fitminFor minimum time domain span；
Mobile module, in the stable region final election starting point WstartWith the stable region final election terminal WendBetween when
Domain span is less than fitminWhen, the mobile stable region final election starting point WstartAnd/or the stable region final election terminal Wend, make to stablize
Area's final election starting point WstartWith the stable region final election terminal WendBetween the time domain span reach fitmin。
Systems for optical inspection disclosed in third aspect present invention, including the light-source system for being irradiated to reaction cup, use
In the processor for receiving the receiver through the transmitted light of the reaction cup and being connected with the receiver, sample suction is being carried out
When the analysis of light varience rate, the processor executes following operation:
1) time series data of the processor acquisition is obtained, and the time series data point in predetermined interval is fitted, is obtained
To absorbance curve；
2) primary election is stablized the tentative starting point A of reaction phase and is fixed tentatively eventually on the absorbance curve in the predetermined interval
Point M, and obtained on the absorbance curve between the tentative starting point A and the tentative terminal M and meet the first default item
The point N of part, first preset condition are as follows: the tangent slope of the excessively described point N is equal to the tentative starting point A and the tentative terminal
The line slope D of M1；
3) final election starting point W is determined between the tentative starting point A and the point Nstart；In the point N and the tentative end
Final election terminal W is determined between point Mend。
4) the final election starting point W is chosenstartWith the final election terminal WendBetween the time series data point analysis sample inhale
Light varience rate.
The analysis method of sample absorbance change rate disclosed in this invention first selects the tentative starting point of stable reaction phase
A and tentative terminal M, then finds point N, the searching foundation of point N between tentative starting point A and tentative terminal M are as follows:
The line slope D of tentative starting point A and tentative terminal M1Represent the absorbance change of the entire stable reaction phase of primary election
Mean Speed finds tangent slope equal to D according to Lagrange mean value theorem on absorbance curve1Point N, then can be true
Fixed point N, which is in, to be stablized in the reaction phase；
Final election starting point W is redefined between tentative starting point A and point Nstart, final election is determined between point N and tentative terminal M
Terminal Wend。
For compared with the prior art, the segment in the present invention for calculating sample absorbance change rate includes in guarantee
Under the premise of having the point N equal with average response rate, the section for calculating sample absorbance change rate is also effectively shortened
Section, this just eliminates initial reaction phase on absorbance curve and the time series data point in reaction was completed phase as far as possible, to improve
The reliability of the analysis result of sample absorbance change rate.
Detailed description of the invention
Fig. 1 is the division schematic diagram in current absorbance curve to sample each reaction phase；
Fig. 2 is the flow diagram of the analysis method of sample absorbance change rate disclosed in the embodiment of the present invention；
Fig. 3 is the flow diagram of the analysis method of sample absorbance change rate disclosed in an embodiment of the present invention；
Fig. 4 is the flow diagram of the analysis method of sample absorbance change rate disclosed in another embodiment of the present invention；
Fig. 5 is the flow diagram of the analysis method of sample absorbance change rate disclosed in further embodiment of this invention；
Fig. 6 is that the absorbance curve that obtains in two-dimensional coordinate system moves towards schematic diagram；
Fig. 7 is the selection schematic diagram that starting point A and tentative terminal M are fixed tentatively in an embodiment of the present invention；
Fig. 8 is the selection schematic diagram of midpoint of embodiment of the present invention N；
Fig. 9 is the structural schematic diagram of the Systems for optical inspection disclosed in the embodiment of the present invention.
Wherein 1 is light source, and 2 be lens, and 3 be optical filter, and 4 be optical fiber, and 5 be reaction cup, and 6 be receiver.
Specific embodiment
Disclosed in this invention the analysis method of sample absorbance change rate can be applied to medical science or change
In work detection field, certainly, in addition to the two fields, which can also be used in other experimental fields, and the present invention is to above-mentioned
The application field of analysis method is simultaneously not specifically limited.
Above-mentioned analysis method is described in detail so that medical domain is to the detection of sample as an example below.
The analysis method of sample absorbance change rate in the present embodiment, is primarily adapted for use in turbidimetry, below in conjunction with
Technical solution of the present invention is described in detail in specific embodiment and attached drawing.
Please first refering to fig. 2, disclosed in this invention sample absorbance change rate analysis method, including following step
It is rapid:
SA): the time series data point in predetermined interval is fitted, absorbance curve is obtained；
SB) on the absorbance curve in the predetermined interval primary election stablize the tentative starting point A of reaction phase and tentative
Terminal M, and it is default that satisfaction first is obtained on the absorbance curve between the tentative starting point A and the tentative terminal M
The point N of condition, first preset condition are as follows: the tangent slope of the excessively described point N is equal to the tentative starting point A and the tentative end
The line slope D of point M1；
SC) final election starting point W is determined between the tentative starting point A and the point Nstart；In the point N and the tentative end
Final election terminal W is determined between point Mend, in embodiments of the present invention, final election starting point WstartWith final election terminal WendAcquisition can have
Various ways, as long as guaranteeing final election starting point WstartWith final election terminal WendSelection can remove as far as possible influence absorbance change rate
The time series data point of accuracy；
SD) choose the final election starting point WstartWith the final election terminal WendBetween the time series data point analysis sample
Absorbance change rate needs to be illustrated, can be using including performance rate method when analyzing sample absorbance change rate
With the various analysis including two-point method.
For compared with the prior art, guaranteeing in above-described embodiment for calculating the segment of sample absorbance change rate
Under the premise of including the point N equal with average response rate, also effectively shorten for calculating sample absorbance change rate
Segment, this just eliminates initial reaction phase on absorbance curve and the time series data point in reaction was completed phase as far as possible, thus
Improve the reliability of the analysis result of sample absorbance change rate.
The present invention program is described in detail in a manner of independent specific embodiment individually below.
First embodiment please refers to Fig. 3:
In the present embodiment, sample absorbance change rate analysis method the following steps are included:
1) the time series data point in predetermined interval is fitted to obtain absorbance curve y=f (x)；
This step is specifically to carry out in absorbance-time coordinate system (alternatively referred to as two-dimensional coordinate system), this step is specific
S1, S2 in respective figure 3, absorbance-time coordinate system abscissa are the time, and ordinate is absorbance, time series data point
Acquisition modes be conventional means, the acquisition modes at following clock synchronization ordinal number strong point are described briefly:
Referring to FIG. 9, Fig. 9 is a kind of Systems for optical inspection, it is made of light source 1, lens 2, optical filter 3 and optical fiber 4
Light-source system be located at the side of reaction cup, the light that light source is issued is radiated in reaction cup 5, is placed in reaction cup 5
The sample to be examined reacted is radiated on receiver 6 through the light after reaction cup, the signal acquisition circuit in receiver 6
The light quantity received is converted into transmitted light intensity, according to Lambert-Beer (Lambert-Beer) law:
The absorbance at each acquisition moment, I in formula can be calculated according to incident intensity and transmitted light intensity0Represent incident intensity, ItGeneration
The output intensity of table t moment, A represent absorbance, and the time interval at two neighboring acquisition moment is t (example during actually detected
Such as 0.1s), the acquisition through (such as 140s) after a period of time, so that it may form multiple data points in absorbance-time coordinate system；
For different samples, the predetermined interval for carrying out data fitting might have difference, predetermined interval usually by
Stablize the experience starting point of reaction phase to the last one the time series data point for adopting assembling process, certainly, those skilled in the art
Above-mentioned predetermined interval can be adjusted.
Continuous absorbance curve can be formed after being fitted to the time series data point in predetermined interval, as shown in Figure 6,
Absorbance curve is the function the most suitable chosen from the function model prestored, skilled artisans appreciate that
It is, if the curvature of the data point on absorbance curve need to be obtained, to need to guarantee that absorbance curve has second dervative, in order to
Curvature in subsequent step solves；
2) on the absorbance curve in predetermined interval primary election stablize the reaction phase tentative starting point A and tentative terminal M, and
The point N for meeting the first preset condition is obtained on the absorbance curve between tentative starting point A and tentative terminal M, wherein first
Preset condition are as follows: the tangent slope of the excessively described point N is equal to the line slope D of the tentative starting point A and the tentative terminal M1；
Step in the specific respective figure 3 of this step: the abscissa of the tentative starting point A of reaction phase is stablized in S34, S5, primary election
For xa, the abscissa for fixing tentatively terminal M is xm；
The tentative starting point A that the reaction phase is stablized in primary election can usually fix tentatively for stablize the experience starting point of reaction phase (i.e. with it is predetermined
The starting point in section is identical)；Tentative terminal M can fix tentatively to stablize the experience end point of reaction phase, calculate tentative starting point A and fix tentatively eventually
The line slope D of point M1And find point N；
In this step, the slope D of tentative starting point A Yu tentative terminal M line need to be calculated first1, in Lagrange
It is worth theorem (Lagrange Mean Value Theorem, also known as Order Derivatives in Differential Mid-Value Theorem) it was determined that in tentative starting point A and temporarily
Determine to there will necessarily be point a N, abscissa x on the curve between terminal Mn, tangent slope of the absorbance curve at point N be equal to
D1, as shown in Figure 8, finding for point N can be realized by calculating the first derivative of absorbance curve, it is, of course, also possible to using it
His mode finds point N.
3) final election starting point W is determinedstart:
Between tentative starting point A and point N, meet the point P of the second preset condition if it exists, then it will be nearest with point N distance
Point P is recorded as final election starting point Wstart, second preset condition are as follows: the curvature k of point PpMeet condition | kn-kp| > R, R are to determine
Threshold value, knFor the curvature of point N；
Determine final election terminal Wend:
Final election terminal W is determined between point N and tentative terminal Mend；
The subsequent judgement assignment procedure of step S6, S61, S7 and S7 in the step corresponding diagram 3；
Since absorbance curve y=f (x) has second dervative, pass through curvature estimation formula
The curvature k of N point can be calculatedn；
In section [xa, xn] in, along X-axis reverse (to the left) with interval t since point N1(it is equal with sampling time interval t or
Differ) be step pitch node-by-node algorithm absorbance curve on corresponding points P curvature kP, meet condition if it exists | kn-kp| the correspondence of > R
Point P, then will be in the first fit along the reverse moving process of X-axis | kn-kp| the corresponding points P of > R (i.e. with point N apart from nearest point P)
It is recorded as stablizing the final election starting point W of reaction phasestart, meet condition if it does not exist | kn-kp| the corresponding points P of > R, then it will be described temporary
Determine starting point A to be recorded as stablizing the final election starting point W of reaction phasestart, wherein R is decision threshold.
It needs to be illustrated, decision threshold R has different values, usual situation according to different absorbance curves
Lower decision threshold R can be stored in the database, and decision threshold R can increase or contract according to the difference of precise requirements
It is small；
Determine final election terminal Wend；
Final election terminal W is determined between point N and tentative terminal M (including endpoint)end, in the present embodiment, directly will point N
It is recorded as the final election terminal Wend。
4) final election starting point W is chosenstartWith final election terminal WendBetween time series data point analysis sample absorbance change rate.
Step S9 in the step corresponding diagram 3 chooses final election starting point WstartWith final election terminal WendBetween time series data
Point, and clock synchronization ordinal number strong point carries out linear (such as least square method) fitting, the straight slope D after fitting is then calculated0, root
According to straight slope D0The change rate of extinction degree per second is represented, according to actual needs, by straight slope D0It is every to be converted into absorbance
Minute change rate or per hour change rate.Certainly, gradient descent method, gauss-newton method etc. can also be used in linear fit,
This is not specifically limited in the present invention.
Due to final election starting point WstartWith final election terminal WendBetween time series data point be in the stable reaction phase, therefore
In final election starting point WstartWith final election terminal WendBetween can also be used two-point method calculate absorbance change rate.
Compared to the current determination method for stablizing the reaction phase, the analysis side of sample absorbance change rate disclosed in this invention
Method first selects the tentative starting point A and tentative terminal M of stable reaction phase, then carries out final election to tentative starting point A again and obtains final election
Starting point Wstart, final election is carried out to tentative terminal M and obtains final election terminal Wend；
Carry out final election starting point WstartFoundation are as follows:
The line slope D of tentative starting point A and tentative terminal M1Represent the absorbance change of the entire stable reaction phase of primary election
Mean Speed finds tangent slope equal to D according to Lagrange mean value theorem on absorbance curve1Point N, then can be true
Fixed point N, which is in, to be stablized in the reaction phase, and the curvature k of point N is calculatednIf there is point P between tentative starting point A and point N, point P's
Curvature kpMeet condition | kn-kp| > decision threshold R then proves at point P as inflection point, using with point N apart from nearest P point as answering
Select starting point WstartIt can be by tentative starting point A and final election starting point WstartBetween the initial reaction phase removal；
And since point N was inherently in the stable reaction phase, N point is recorded as final election terminal WendIt can guarantee multiple
Select starting point WstartWith final election terminal WendBetween time series data point be in the stable reaction phase, therefore choose final election starting point
WstartWith the final election terminal WendBetween time series data point analysis sample absorbance change rate is analyzed can make minute
It is more accurate reliable to analyse result.
Second embodiment:
The step of being identical with the first embodiment no longer is repeated in the present embodiment, compared with first embodiment, this reality
The difference for applying example essentially consists in final election terminal WendDetermination method, after the step S7 ' and step S7 ' in Fig. 4
Assignment procedure, specifically, meet the point q of third preset condition if it exists between point N and tentative terminal M, then it will be with the point
The nearest point q of N distance is recorded as stablizing the final election terminal W of reaction phaseend, wherein the third preset condition are as follows: described
The curvature k of point qqMeet condition | kn-kq| > R, R are decision threshold, knFor the curvature of point N.
In actual mechanical process, in section [xn, xm] in, along X-axis positive (to the right) with interval t since point N1(with sampling
Time interval t is equal or different) be step pitch node-by-node algorithm absorbance curve on corresponding points q curvature kq, meet condition if it exists |
kn-kq| the corresponding points q of > R, then will be in the first fit along X-axis forward direction moving process | kn-kq| > R corresponding points q (i.e. with point
N is recorded as stablizing the final election terminal W of reaction phase apart from nearest point q)end, meet condition if it does not exist | kn-kq| the correspondence of > R
The tentative terminal M is then recorded as stablizing the final election terminal W of reaction phase by point qend, wherein R is decision threshold.
Similarly, decision threshold R has different values according to different absorbance curves, under normal conditions the decision threshold
R can be stored in the database, and decision threshold R can increase or reduce according to the difference of precise requirements.
In above-mentioned two embodiment, the selection for stablizing the tentative starting point A and tentative terminal M of reaction phase is empirically to rise
What initial point and experience end point carried out, the tentative starting point that the reaction phase is stablized in another primary election is also disclosed in the embodiment of the present invention
The method of A and tentative terminal M, please refer to Fig. 5:
3rd embodiment:
The step identical as above-mentioned two embodiment is no longer repeated in the present embodiment, side disclosed in the present embodiment
The main difference of case and above-mentioned two embodiment is the selection method of tentative terminal M, please refers to step S3, S4 in Fig. 5, selects
Last collected time series data point B is taken, according to sample type, chooses the experience starting point for stablizing the reaction phase as tentative starting point
A, the line slope for fixing tentatively starting point A and time series data point B is D2, tangent slope is found on absorbance curve equal to D2Point, and
Using the point as the tentative terminal M.
Referring to FIG. 7, step S4 foundation be Lagrange mean value theorem (Lagrange Mean Value Theorem,
Also known as Order Derivatives in Differential Mid-Value Theorem), it there will necessarily be a point M, abscissa on fixing tentatively the curve between starting point A and time series data point B
For xm, tangent slope of the absorbance curve at point M is equal to D2, understood incorporated by reference to Fig. 6, fix tentatively starting point A and time series data point
The line slope of B represents the Mean Speed in entire sample reaction process substantially, and the slope of string AM is the first half of reaction process
The Mean Speed divided, the slope of string MB are the Mean Speed of part after reaction process, and after reaction process partially substantially
The response curve between tentative starting point A and tentative terminal M is selected as tentative terminal within reaction was completed phase, therefore by point M
The stabilization reaction phase as primary election can guarantee sample absorbance change rate precision of analysis.
In order to advanced optimize scheme, (the step S8 of attached drawing 4-5 between the step 3) and step 4) of the various embodiments described above
Between step S9) it further comprises the steps of:
31) in final election starting point WstartWith final election terminal WendBetween time domain span (final election starting point i.e. in time reference axis
WstartWith final election terminal WendSpan) be less than fitminWhen, force mobile final election starting point WstartAnd/or final election terminal Wend, with
Just make final election starting point WstartWith the final election terminal WendBetween time domain span number reach fitmin, wherein fitminFor minimum
Time domain span is substantially the minimal linear regression time (such as 10 seconds, 15 seconds or 20 seconds) of setting, be arranged minimum time domain across
The purpose of degree is to guarantee final election starting point WstartWith final election terminal WendBetween have enough time series data points, to protect
The reliability of card analysis result.It will be appreciated by persons skilled in the art that fitminNeed the difference according to fitting function type
Carry out adaptive settings, it is generally the case that fitminThe computational solution precision highest obtained under a certain numerical value, fitminValue
The excessive or too small precision that can reduce calculated result.
More specifically, in final election starting point WstartWith final election terminal WendBetween time domain span be less than fitminWhen, it forces
Mobile final election starting point WstartAnd/or final election terminal WendA kind of method are as follows:
Calculate final election starting point WstartWith the time domain span L between tentative starting point A1It (can be by seeking final election starting point Wstart's
The difference of the abscissa of abscissa and tentative starting point A is realized)；Calculate tentative terminal M and final election terminal WendTime domain span L2
It (can be by seeking tentative terminal M and final election terminal WendAbscissa difference realize), if L1< L2, then (such as with predetermined step pitch
0.1s) force the mobile final election terminal W (i.e. along X-axis forward direction) to the rightend；If L1> L2, then forced with predetermined step pitch to the left (i.e. along X
Axis is reverse) movement final election starting point WstartIf L1=L2, then final election terminal W symmetrically (is moved along X-axis forward direction with predetermined step pitchend, i.e.,
Final election starting point W is inversely moved along X-axisstart) force mobile final election starting point WstartWith final election terminal Wend, so that final election starting point Wstart
With the final election terminal WendBetween time domain span reach fitmin。
In addition to this, another is also disclosed in the embodiment of the present invention forces mobile final election starting point WstartAnd/or final election
Terminal WendMethod:
Obtain the final election terminal WendWith the time domain span L between the tentative starting point A, if L >=fitmin, then with predetermined
Step pitch (such as 0.1s or other times interval) inversely moves the final election starting point W along X-axisstart, when reaching L=fitminWhen, then
Stop final election starting point WstartMovement；If L < fitmin, then (moved further or moving several times with predetermined step pitch) institute is moved
State final election starting point WstartThe extremely tentative starting point A, and the final election terminal W is moved along X-axis forward direction with predetermined step pitchend, Zhi Daosuo
State tentative starting point A and the final election terminal WendBetween time domain span reach fitminWhen just stop the mobile final election terminal
Wend。
It will be appreciated by those skilled in the art that in analysis method disclosed in above-described embodiment, when concentration of specimens is lower
When, the overall curvature of corresponding absorbance curve is smaller, therefore the final section chosen for the calculating of absorbance change rate
[Wstart, Wend] larger, for calculated absorbance change rate closer to ensemble average value, this can be substantially reduced the coefficient of variation；
And when concentration of specimens is higher, the overall curvature of corresponding absorbance curve is larger, final to choose based on absorbance change rate
Section [the W of calculationstart, Wend] smaller, this can effectively remove the inflection point in the stable reaction phase, to improve absorbance change rate
Accuracy.As it can be seen that no matter the height of concentration of specimens, for current performance rate method, disclosed in the embodiment of the present invention
Analysis method can effectively improve the computational accuracy of absorbance change rate.
In addition to this, a kind of sample absorbance change rate acquisition device is also disclosed in the embodiment of the present invention comprising:
Fitting module obtains absorbance curve for being fitted to the time series data point in predetermined interval；
Stablize and react initial modeling block, reaction is stablized in primary election on the absorbance curve in the predetermined interval
The tentative starting point A and tentative terminal M of phase；
First median point obtains module, for the absorbance between the tentative starting point A and the tentative terminal M
The point N for meeting the first preset condition, first preset condition are obtained on curve are as follows: the tangent slope of the excessively described point N is equal to institute
State the line slope D of tentative starting point A Yu the tentative terminal M1；
Final election starting point obtains module, for obtaining final election starting point W between the tentative starting point A and the point Nstart；
Final election terminal obtains module, for obtaining final election terminal W between the point N and the tentative terminal Mend；
Absorbance change rate analysis module, for choosing the final election starting point WstartWith the final election terminal WendBetween
The data point analysis sample absorbance change rate.
In above-mentioned acquisition device, include and average response for calculating the segment of sample absorbance change rate guaranteeing
Under the premise of the equal point N of rate, the segment for calculating sample absorbance change rate is also effectively shortened, this just goes as far as possible
In addition to the time series data point in initial reaction phase on absorbance curve and reaction was completed phase, to improve the change of sample absorbance
The reliability of the analysis result of rate.
Further, acquisition dress on the basis of above-mentioned absorbance change rate analytical equipment, disclosed in the present embodiment
It sets further include:
Second Intermediate Value obtains module, between the tentative starting point A and the last collected time series data point B
The absorbance curve on obtain tangent slope be equal to D2Point, and by the point be recorded as the tentative terminal M for it is described just
Modeling block uses, wherein D2For the line slope of the tentative starting point A and the time series data point B.
Increase Second Intermediate Value obtain module after, fix tentatively terminal M acquisition modes can according to Lagrange mean value theorem into
Row, for directlying adopt the case where experience end point is as tentative terminal M, tentative terminal M selected by this kind of mode
It is more accurate.
In order to final election starting point WstartWith final election terminal WendBetween data point number judged and compared, this implementation
The analytical equipment of sample absorbance change rate disclosed in example advanced optimizes on the basis of the above embodiments, this reality
Apply the acquisition device in example further include:
Comparison module is used for the stable region final election starting point WstartWith the stable region final election terminal WendBetween
Whether time domain span is less than fitmin, wherein fitminFor minimum time domain span；
Mobile module, in the stable region final election starting point WstartWith the stable region final election terminal WendBetween when
Domain span is less than fitminWhen, the mobile stable region final election starting point WstartAnd/or the stable region final election terminal Wend, make to stablize
Area's final election starting point WstartWith the stable region final election terminal WendBetween the time domain span reach fitmin。
A kind of Systems for optical inspection is also disclosed in the embodiment of the present invention, as shown in Figure 9, including for shining reaction cup
The light-source system penetrated, the receiver for receiving the transmitted light for passing through reaction cup and the processor being connected with receiver, into
When row detection, which executes following operation:
1) time series data of processor acquisition is obtained, and the time series data point in predetermined interval is fitted, is inhaled
Luminosity curve；
2) on the absorbance curve in predetermined interval primary election stablize the reaction phase tentative starting point A and tentative terminal M, and
The point N for meeting the first preset condition, the first preset condition are obtained on absorbance curve between tentative starting point A and tentative terminal M
Are as follows: the tangent slope for crossing point N is equal to the line slope D of tentative starting point A and tentative terminal M1；
3) final election starting point W is determined between tentative starting point A and point Nstart；Determine that final election is whole between point N and tentative terminal M
Point Wend；
4) final election starting point W is chosenstartWith final election terminal WendBetween time series data point analysis sample absorbance change rate.
As shown in Figure 9, the light-source system that light source 1, lens 2, optical filter 3 and optical fiber 4 are constituted is located at reaction cup
Side, the light that light source is issued are radiated in reaction cup 5, and the sample to be examined reacted is placed in reaction cup 5, are penetrated
Light after reaction cup 5 is radiated on receiver 6, and the signal acquisition circuit in receiver 6 is converted to the light quantity received
Penetrate light intensity.According to Lambert-Beer's law, the extinction at each acquisition moment can be calculated according to incident intensity and transmitted light intensity
Degree, the time interval at two neighboring acquisition moment is t (such as 0.1s) during actually detected, through (such as 140s) after a period of time
Acquisition, so that it may multiple data points are formed in two-dimensional coordinate system.Then the analysis in above-mentioned steps is executed by processor
Method calculates sample absorbance change rate.
Point of sample absorbance change rate as disclosed in above-mentioned Systems for optical inspection is able to carry out above-described embodiment
Analysis method, therefore the Systems for optical inspection has the corresponding technological merit of above-mentioned analysis method, no longer goes to live in the household of one's in-laws on getting married to this herein
It states.
Above to analysis method, analytical equipment and the Systems for optical inspection of sample absorbance change rate disclosed in this invention
It is described in detail.Used herein a specific example illustrates the principle and implementation of the invention, the above reality
The explanation for applying example is merely used to help understand method and its core concept of the invention.It should be pointed out that for the art
For those of ordinary skill, without departing from the principle of the present invention, can with several improvements and modifications are made to the present invention,
These improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (15)
1. a kind of analysis method of sample absorbance change rate characterized by comprising
1) the time series data point in predetermined interval is fitted, obtains absorbance curve；
2) on the absorbance curve in the predetermined interval primary election stablize the reaction phase tentative starting point A and tentative terminal M,
And it is obtained on the absorbance curve between the tentative starting point A and the tentative terminal M and meets the first preset condition
Point N, first preset condition are as follows: the tangent slope of the excessively described point N is equal to the tentative starting point A's and tentative terminal M
Line slope D1；
3) final election starting point W is determined between the tentative starting point A and the point Nstart；The point N and the tentative terminal M it
Between determine final election terminal Wend；
4) the final election starting point W is chosenstartWith the final election terminal WendBetween the time series data point analysis sample absorbance
Change rate.
2. analysis method according to claim 1, which is characterized in that in the step 3), determine the final election starting point
WstartMethod are as follows:
Between the tentative starting point A and the point N, meet the point P of the second preset condition if it exists, then will with the point N away from
Final election starting point W is recorded as from the nearest point Pstart, second preset condition are as follows: the curvature k of the point PpMeet condition |
kn-kp| > R, R are decision threshold, knFor the curvature of point N.
3. analysis method according to claim 1, which is characterized in that in the step 3), determine the final election terminal
WendMethod are as follows: the point N is recorded as the final election terminal Wend。
4. analysis method according to claim 1, which is characterized in that in the step 3), determine the final election terminal
WendMethod are as follows:
Between the point N and the tentative terminal M, meet the point q of third preset condition if it exists, then will with the point N away from
It is recorded as stablizing the final election terminal W of reaction phase from the nearest point qend, wherein the third preset condition are as follows: the point q
Curvature kqMeet condition | kn-kq| > R, R are decision threshold, knFor the curvature of point N.
5. analysis method according to claim 2, which is characterized in that in the step 3), if it does not exist described in satisfaction
The point P of second preset condition, then using the tentative starting point A as final election starting point Wstart。
6. analysis method according to claim 4, which is characterized in that in the step 3), meet third if it does not exist
The point q of preset condition, then using the tentative terminal M as the final election terminal Wend。
7. analysis method according to claim 1, which is characterized in that in the step 2), the reaction phase is stablized in primary election
The method of tentative starting point A and tentative terminal M are as follows:
Last collected time series data point B is chosen, according to sample type, chooses the experience starting point for stablizing the reaction phase as institute
The line slope for stating tentative starting point A, the tentative starting point A and the time series data point B is D2, looked on the absorbance curve
It is equal to D to tangent slope2Point, and using the point as the tentative terminal M.
8. analysis method according to claim 1, which is characterized in that between the step 3) and the step 4), also
Comprising steps of
31) in the final election starting point WstartWith the final election terminal WendBetween time domain span be less than fitminWhen, force movement
The final election starting point WstartAnd/or the final election terminal Wend, make the final election starting point WstartWith the final election terminal WendBetween
Time domain span reach fitmin, wherein fitminFor minimum time domain span.
9. analysis method according to claim 8, which is characterized in that force the mobile final election starting point WstartAnd/or institute
State final election terminal WendMethod are as follows:
Obtain the final election starting point WstartThe time domain span L between the tentative starting point A1；Obtain the tentative terminal M with
The final election terminal WendBetween time domain span L2If L1< L2, then positive to move the final election terminal Wend；If L1> L2, then
Inversely move the final election starting point WstartIf L1=L2, then the final election starting point W is symmetrically movedstartWith the final election terminal
Wend。
10. analysis method according to claim 8, which is characterized in that force the mobile final election starting point WstartAnd/or institute
State final election terminal WendMethod are as follows:
Obtain the final election terminal WendWith the time domain span L between the tentative starting point A, if L >=fitmin, then institute is inversely moved
State final election starting point Wstart；If L < fitmin, then the final election starting point W is inversely movedstartThe extremely tentative starting point A, and positive shifting
Move the final election terminal Wend, so that the final election starting point WstartWith the final election terminal WendBetween time domain span reach
fitmin。
11. analysis method described in -10 any one according to claim 1, which is characterized in that in the step 4), to institute
State final election starting point WstartWith the final election terminal WendBetween the time series data point carry out linear fit, and be calculated quasi-
Straight slope D after conjunction0, according to the straight slope D0Obtain sample absorbance change rate.
12. a kind of analytical equipment of sample absorbance change rate characterized by comprising
Fitting module obtains absorbance curve for being fitted to the time series data point in predetermined interval；
Stablize and react initial modeling block, the reaction phase is stablized in primary election on the absorbance curve in the predetermined interval
Tentative starting point A and tentative terminal M；
First median point obtains module, for the absorbance curve between the tentative starting point A and the tentative terminal M
It is upper to obtain the point N for meeting the first preset condition, first preset condition are as follows: the tangent slope of the excessively described point N is equal to described temporary
Determine the line slope D of starting point A Yu the tentative terminal M1；
Final election starting point obtains module, for obtaining final election starting point W between the tentative starting point A and the point Nstart；
Final election terminal obtains module, for obtaining final election terminal W between the point N and the tentative terminal Mend；
Absorbance change rate analysis module, for choosing the final election starting point WstartWith the final election terminal WendBetween it is described
Data point analysis sample absorbance change rate.
13. analytical equipment according to claim 12, which is characterized in that further include:
Second Intermediate Value point obtains module, between the tentative starting point A and the last collected time series data point B
Tangent slope is obtained on the absorbance curve is equal to D2Point, and the point is recorded as the tentative terminal M for the primary election
Module uses, wherein D2For the line slope of the tentative starting point A and the time series data point B.
14. analytical equipment according to claim 13, which is characterized in that further include:
Comparison module is used for the stable region final election starting point WstartWith the stable region final election terminal WendBetween time domain
Whether span is less than fitmin, wherein fitminFor minimum time domain span；
Mobile module, in the stable region final election starting point WstartWith the stable region final election terminal WendBetween time domain across
Degree is less than fitminWhen, the mobile stable region final election starting point WstartAnd/or the stable region final election terminal Wend, answer stable region
Select starting point WstartWith the stable region final election terminal WendBetween the time domain span reach fitmin。
15. a kind of Systems for optical inspection, including for being irradiated to reaction cup light-source system, for receiving penetrate the reaction cup
Transmitted light receiver and the processor that is connected with the receiver, which is characterized in that carrying out sample absorbance change
When the analysis of rate, the processor executes following operation:
1) time series data of the processor acquisition is obtained, and the time series data point in predetermined interval is fitted, is inhaled
Luminosity curve；
2) on the absorbance curve in the predetermined interval primary election stablize the reaction phase tentative starting point A and tentative terminal M,
And it is obtained on the absorbance curve between the tentative starting point A and the tentative terminal M and meets the first preset condition
Point N, first preset condition are as follows: the tangent slope of the excessively described point N is equal to the tentative starting point A's and tentative terminal M
Line slope D1；
3) final election starting point W is determined between the tentative starting point A and the point Nstart；The point N and the tentative terminal M it
Between determine final election terminal Wend；
4) the final election starting point W is chosenstartWith the final election terminal WendBetween the time series data point analysis sample absorbance
Change rate.
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| CN116242805A (en) * | 2023-02-03 | 2023-06-09 | 温州泛波激光有限公司 | Laser detection method, laser detection device, and computer storage medium |
| CN116242805B (en) * | 2023-02-03 | 2024-01-23 | 温州泛波激光有限公司 | Laser detection method, laser detection device, and computer storage medium |
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