CN106290675A - Spectral peak terminal method of adjustment and have spectral peak terminal adjust function chromatographic work station - Google Patents
Spectral peak terminal method of adjustment and have spectral peak terminal adjust function chromatographic work station Download PDFInfo
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Abstract
The present invention discloses a kind of spectral peak terminal method of adjustment and has the chromatographic work station of spectral peak terminal adjustment function, comprises determining that spectral peak intermediate point step；Slope value reversion detecting step；As there is not reversion, in lookup group, the G-bar absolute value of data point is less than the first data set of predetermined slope threshold value, and selects any data point in the first data set to make the first data point；Continue to search for N continuous the data set after the first data set, it is judged that slope reversion does not the most occur in the total data the point whether absolute value of the G-bar of N continuous data set is respectively less than in predetermined slope threshold value, and N continuous data set；In this way, last data set in N continuous data set is made the second data set, last data point in the second data set is made the second data point, and selects the data point that the amplitude between the first data point and the second data point is minimum to make spectral peak terminal.Limit and search N number of data set continuously, solve spectral peak final position and determine problem to the rear.
Description
Technical field
The present invention relates to chromatographic techniques field, particularly relate to a kind of spectral peak terminal method of adjustment and there is the chromatographic work station of spectral peak terminal adjustment function.
Background technology
The chromatogram arrangement of industry is provided with chromatographic work station at present, chromatographic work station is equivalent to a host computer, on the one hand the control to slave computer (i.e. chromatogram arrangement) is completed, on the other hand the chromatographic data collected slave computer is analyzed processing, to reach the quantitative analysis to testing sample.Chromatogram arrangement includes chromatograph of liquid, high performance liquid chromatograph and Ultra Performance Liquid Chromatography instrument etc..
Quantitative analysis to testing sample depends on peak area or the peak height of sample correspondence spectral peak.The peak area of spectral peak refers to the area of the figure that spectral peak and baseline surrounded, and before calculating spectral peak area, need first to carry out spectral peak identification, spectral peak identification mainly identifies the beginning and end of spectral peak, the beginning and end only determining spectral peak just can determine that the figure that spectral peak and baseline surround, and finally could calculate spectral peak area.
Number of patent application be the Chinese invention patent application of 201310698160.3 be an earlier application of present applicant, this application is claimed a kind of method identifying spectral peak terminal, with reference to Fig. 1, it is shown that the method flow diagram of this identification spectral peak terminal.The method, solves the method only applying slope threshold value to judge in prior art to identify spectral peak terminal, causes spectral peak terminal to determine inaccurate technical problem, and particularly with the peak that some symmetry are bad, effect becomes apparent from.
Summary of the invention
In follow-up continuous application, we have found that, when testing sample be alkalescence, testing sample sample size is excessive, need to change the situations such as chromatographic column, pipeline do not connect or dead volume is excessive occur time, utilize prior art to determine that spectral peak terminal time is long and spectral peak final position determines the problems such as to the rear determining that spectral peak terminal there will be.With reference to Fig. 2, test finds, when there is above-mentioned multiple situation, the hangover at peak can be the longest, when performing prior art step S104, needs the data that traversal is very many, just can find the second data point, so long time can be wasted, and easily spectral peak final position be determined to the rear.
It is an object of the invention to: solve, in prior art, for the longer peak that trails, to utilize the method for prior art to occur determining that spectral peak terminal time is long and spectral peak final position determines the technical problems such as to the rear, it is provided that a kind of spectral peak terminal method of adjustment.
The spectral peak terminal method of adjustment that the present invention provides, comprises the steps:
Step S301, determines spectral peak intermediate point；
Step S302, whether the slope value of the data point in data set after judging described spectral peak intermediate point successively there is reversion, if there is reversion, using first data point after last data point before reversion or reversion as spectral peak terminal；
Step S303, without reversion occur, in lookup group, the G-bar absolute value of data point is less than the first data set of predetermined slope threshold value, and selects any data o'clock in described first data set as the first data point；
Step S304, continue to search for N continuous the data set after described first data set, judge that slope reversion does not the most occur in the total data the point whether absolute value of the G-bar of described N continuous data set is respectively less than in predetermined slope threshold value, and described N continuous data set；
Step S305, if, then using last data set in described N continuous data set as the second data set, using last data point in described second data set as the second data point, and select data point that the amplitude between described first data point and described second data point is minimum as spectral peak terminal.
Limit and search N number of data set continuously, solve spectral peak final position and determine problem to the rear, save the time determining spectral peak terminal simultaneously.
Illustrate as one, also include step S306, if not, in group after then searching described first data set, the G-bar absolute value of data point is more than a data set of described predetermined slope threshold value, and using this data set as the second data set, select any data o'clock in described second data set as the second data point；Search all data points less than described predetermined slope threshold value of the slope absolute value between described first data point and described second data point, data point minimum for wherein amplitude is defined as spectral peak terminal.
Illustrate as one, in step s 304, if having the data point in one group of data set in described N continuous data set slope reversion occurs, using this group data set as the second data set, and using the data point of slope reversion in this data set as the second data point, and select data point minimum for the amplitude between the first data point and the second data point as spectral peak terminal.
Illustrating as one, N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data, and PW is the peak width of spectral peak, and L is the number of data point in data set.
By above-mentioned equations N value so that spectral peak final position determines and searches for spectral peak terminal time and all reaches optimum.
Illustrating as one, described spectral peak intermediate point is spectral peak summit or spectral peak is turned right a little.
What the method judged first with slope threshold value determined spectral peak turns right a little, reapplies the method identification spectral peak terminal of the present invention, can improve recognition efficiency further.
Another object of the present invention is to: solve in prior art, for the longer peak that trails, the method utilizing prior art occurs determining that spectral peak terminal time is long and spectral peak final position determines the technical problems such as to the rear, it is provided that a kind of chromatographic work station with spectral peak terminal adjustment function.
The chromatographic work station with spectral peak terminal adjustment function disclosed by the invention, including:
Spectral peak intermediate point searches unit, is used for determining spectral peak intermediate point；
Slope value reversion detector unit, whether the slope value of the data point in data set after judging described spectral peak intermediate point successively there is reversion, if there is reversion, using first data point after last data point before reversion or reversion as spectral peak terminal；
First data point searches unit, and for without reversion occur, in lookup group, the G-bar absolute value of data point is less than the first data set of predetermined slope threshold value, and selects any data o'clock in described first data set as the first data point；
Search judging unit, for continuing to search for N continuous the data set after described first data set, judge that slope reversion does not the most occur in the total data the point whether absolute value of the G-bar of described N continuous data set is respectively less than in predetermined slope threshold value, and described N continuous data set；
First terminal point confirmation unit, for under the judged result being, using last data set in described N continuous data set as the second data set, using last data point in described second data set as the second data point, and select data point that the amplitude between described first data point and described second data point is minimum as spectral peak terminal.
Limit and search N number of data set continuously, save the time determining spectral peak terminal, solve spectral peak final position and determine problem to the rear.
Illustrate as one, also include, second terminal confirmation unit, for under no judged result, in group after searching described first data set, the G-bar absolute value of data point is more than a data set of described predetermined slope threshold value, and using this data set as the second data set, select any data o'clock in described second data set as the second data point；Search all data points less than described predetermined slope threshold value of the slope absolute value between described first data point and described second data point, data point minimum for wherein amplitude is defined as spectral peak terminal.
Illustrate as one, in searching judging unit, if having the data point in one group of data set in described N continuous data set slope reversion occurs, using this group data set as the second data set, and using the data point of slope reversion in this data set as the second data point, and select data point minimum for the amplitude between the first data point and the second data point as spectral peak terminal.
Illustrating as one, N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data, and PW is the peak width of spectral peak, and L is the number of data point in array.
By above-mentioned equations N value so that spectral peak final position determines and searches for spectral peak terminal time and all reaches optimum.
Illustrating as one, described spectral peak intermediate point is spectral peak summit or spectral peak is turned right a little.
What the method judged first with slope threshold value determined spectral peak turns right a little, reapplies the method identification spectral peak terminal of the present invention, can improve spectral peak recognition efficiency further.
Accompanying drawing explanation
Fig. 1 is a kind of method flow diagram identifying spectral peak terminal of prior art；
Fig. 2 is the schematic diagram of the spectral peak that a kind of hangover of prior art is grown especially；
Fig. 3 is the method flow diagram of the present invention a kind of spectral peak terminal method of adjustment embodiment；
Fig. 4 is the structural representation of the embodiment of a kind of chromatographic work station 400 with spectral peak terminal adjustment function of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, specific embodiments of the present invention are further described in detail.
With reference to Fig. 3, it is shown that the method flow diagram of the present invention a kind of spectral peak terminal method of adjustment embodiment, comprise the steps:
Step S301, determines spectral peak intermediate point；
In this step, the method that in prior art, slope threshold value judges first is applied to find out the intermediate point of spectral peak.In the present embodiment, the intermediate point of spectral peak is chosen for the summit of spectral peak.
As other citing, the intermediate point of described spectral peak can also choose spectral peak turn right a little or choose spectral peak summit and spectral peak turn right a little between any point as intermediate point.
As other citing, determine that spectral peak intermediate point can also use other prior aries to realize.
Step S302, whether the slope value of the data point in data set after judging described spectral peak intermediate point successively there is reversion, if there is reversion, using first data point after last data point before reversion or reversion as spectral peak terminal；
In this step, slope value occur reversion refer to slope value from negative value become on the occasion of.In the present embodiment, the data point number in each data set is 3, and alternately covers packet, described alternately covering packet refers to: the 1st, 2,3 data points are first group, 2nd, 3,4 data points are second group, and the 3rd, 4,5 data points are the 3rd group, the most alternately cover circulation packet.Choosing every 3 data points is one group, makes spectral peak terminal regulated efficiency height, terminal confirm accurately.
As other citing, the data point number in described each data set can also be 1,2,4 etc..
As other citing, data point number L in described each data set can be according to the formula of prior art:
L=(PW*SR)/15 calculates, in formula: PW is the peak width of spectral peak, and SR is sample rate.
As other citing, each data set can also use other group technologies, and the such as the 1st, 2,3 data points are first group, and the 3rd, 4,5 data points are second group；Or the 1st, 2,3 data points are first group, the 4th, 5,6 data points are second group.
As other citing, there is reversion in described slope value, it is also possible to refer to that slope value is become 0 from negative value.
Step S303, without reversion occur, in lookup group, the G-bar absolute value of data point is less than the first data set of predetermined slope threshold value, and selects any data o'clock in described first data set as the first data point；
In this step, illustrating as one, by described data set, slope absolute value is defined as the first data point less than predetermined slope threshold value and minimum data point.In the case of data in described data set are relatively more, directly slope absolute value is defined as the first data point less than predetermined slope threshold value and minimum data point, it is possible to reduce the time of spectral peak terminal identification.
Step S304, continue to search for N continuous the data set after described first data set, judge that slope reversion does not the most occur in the total data the point whether absolute value of the G-bar of described N continuous data set is respectively less than in predetermined slope threshold value, and described N continuous data set；
Step S305, if, then using last data set in described N continuous data set as the second data set, using last data point in described second data set as the second data point, and select data point that the amplitude between described first data point and described second data point is minimum as spectral peak terminal.
In the present embodiment, amplitude correspondence absorbance, absorbance refers to that light passes through the incident intensity before solution or a certain material and this light denary logarithm by the transmitted intensity ratio after solution or material, and the unit of absorbance is Au, mAu.
The spectral peak terminal method of adjustment of the present embodiment, limits and searches N number of data set continuously, save the time determining spectral peak terminal, solve spectral peak final position and determine problem to the rear.
Illustrate as one, also include step S306, if not, in group after then searching described first data set, the G-bar absolute value of data point is more than a data set of described predetermined slope threshold value, and using this data set as the second data set, select any data o'clock in described second data set as the second data point；Search all data points less than described predetermined slope threshold value of the slope absolute value between described first data point and described second data point, data point minimum for wherein amplitude is defined as spectral peak terminal.
, when there is ascendant trend again in the hangover at peak in embodiment in this illustration, it is possible to determines spectral peak terminal quickly and accurately.
Illustrate as one, in step s 304, if having the data point in one group of data set in described N continuous data set slope reversion occurs, using this group data set as the second data set, and using the data point of slope reversion in this data set as the second data point, and select data point minimum for the amplitude between the first data point and the second data point as spectral peak terminal.
Data point is occurred the data set of slope reversion as the second data set, the time of spectral peak terminal identification can be saved further.
In the present embodiment, N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data, and PW is the peak width of spectral peak, and L is the number of data point in data set.Wherein, before chromatographic signal sampling, need user to set sample rate SR of chromatographic data, before carrying out chromatographic data process, need user to set peak width PW and the predetermined slope threshold value of spectral peak.As other citing, in this illustration, it is also possible to use automatic peak width and automatic threshold, peak width PW of spectral peak and predetermined slope threshold value are just not required to user and set.
By above-mentioned equations N value so that spectral peak final position determines and searches for spectral peak terminal time and all reaches optimum.For same one piece of data, user sets different sample rate SR, peak width PW of spectral peak and predetermined slope threshold values, uses above-mentioned equations N value, all can reach optimum effect.
Illustrating as one, described spectral peak intermediate point is spectral peak summit or spectral peak is turned right a little.
What the method judged first with slope threshold value determined spectral peak turns right a little, reapplies the method identification spectral peak terminal of the present invention, can improve recognition efficiency further.
With reference to Fig. 4, it is shown that the structural representation of the embodiment of a kind of chromatographic work station 400 with spectral peak terminal adjustment function of the present invention.Chromatographic work station 400 includes:
Spectral peak intermediate point searches unit 401, is used for determining spectral peak intermediate point；
Slope value reversion detector unit 402, whether the slope value of the data point in data set after judging described spectral peak intermediate point successively there is reversion, if there is reversion, using first data point after last data point before reversion or reversion as spectral peak terminal；
First data point searches unit 403, and for without reversion occur, in lookup group, the G-bar absolute value of data point is less than the first data set of predetermined slope threshold value, and selects any data o'clock in described first data set as the first data point；
Search judging unit 404, for continuing to search for N continuous the data set after described first data set, judge that slope reversion does not the most occur in the total data the point whether absolute value of the G-bar of described N continuous data set is respectively less than in predetermined slope threshold value, and described N continuous data set；
First terminal point confirmation unit 405, for under the judged result being, using last data set in described N continuous data set as the second data set, using last data point in described second data set as the second data point, and select data point that the amplitude between described first data point and described second data point is minimum as spectral peak terminal.
Limit and search N number of data set continuously, save the time determining spectral peak terminal, solve spectral peak final position and determine problem to the rear.
Illustrate as one, chromatographic work station 400 also includes, second terminal confirmation unit 406, for under no judged result, in group after searching described first data set, the G-bar absolute value of data point is more than a data set of described predetermined slope threshold value, and using this data set as the second data set, select any data o'clock in described second data set as the second data point；Search all data points less than described predetermined slope threshold value of the slope absolute value between described first data point and described second data point, data point minimum for wherein amplitude is defined as spectral peak terminal.
Illustrate as one, in searching judging unit 404, if having the data point in one group of data set that slope reversion occurs in described N continuous data set, using this group data set as the second data set, and using the data point of slope reversion in this data set as the second data point, and select data point minimum for the amplitude between the first data point and the second data point as spectral peak terminal.
Illustrating as one, N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data, and PW is the peak width of spectral peak, and L is the number of data point in array.
By above-mentioned equations N value so that spectral peak final position determines and searches for spectral peak terminal time and all reaches optimum.
Illustrating as one, described spectral peak intermediate point is spectral peak summit or spectral peak is turned right a little.
What the method judged first with slope threshold value determined spectral peak turns right a little, reapplies the method identification spectral peak terminal of the present invention, can improve recognition efficiency further.
Illustrating as one, described chromatographic work station 400 performs each step according to the flow chart shown in Fig. 3.
Above-described only the preferred embodiments of the present invention; it is it should be understood that; the explanation of preferred embodiment above is only intended to help to understand method and the core concept thereof of the present invention; the protection domain being not intended to limit the present invention; any amendment of being made within all thought in the present invention and principle, equivalent etc., should be included within the scope of the present invention.
Claims (10)
1. a spectral peak terminal method of adjustment, comprises the steps:
Step S301, determines spectral peak intermediate point；
Step S302, whether the slope value of the data point in data set after judging described spectral peak intermediate point successively goes out
Existing reversion, if there is reversion, by first data point after last data point before reversion or reversion
As spectral peak terminal；
Step S303, without reversion occur, in lookup group, the G-bar absolute value of data point is oblique less than predetermined
First data set of rate threshold value, and select any data o'clock in described first data set as the first data
Point；
It is characterized in that, also include:
Step S304, continues to search for N continuous the data set after described first data set, it is judged that described N continuous
Whether the absolute value of the G-bar of individual data set is respectively less than predetermined slope threshold value, and described N continuous data
The most there is not slope reversion in total data point in group；
Step S305, if it is, using last data set in described N continuous data set as the second number
According to group, using last data point in described second data set as the second data point, and select described
The minimum data point of amplitude between one data point and described second data point is as spectral peak terminal.
Spectral peak terminal method of adjustment the most according to claim 1, it is characterised in that also include step S306,
If it is not, then the G-bar absolute value of data point is more than described in group after searching described first data set
One data set of predetermined slope threshold value, and using this data set as the second data set, select described second number
According to any data in group o'clock as the second data point；Search described first data point and described second data point
Between slope absolute value less than all data points of described predetermined slope threshold value, by number minimum for wherein amplitude
Strong point is defined as spectral peak terminal.
Spectral peak terminal method of adjustment the most according to claim 1, it is characterised in that in step s 304,
If having the data point in one group of data set in described N continuous data set slope reversion occurs, will
This group data set is as the second data set, and using the data point of slope reversion in this data set as the second data
Point, and select using data point minimum for the amplitude between the first data point and the second data point as spectral peak eventually
Point.
4. according to the spectral peak terminal method of adjustment described in claim 1,2 or 3, it is characterised in that
N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data,
PW is the peak width of spectral peak, and L is the number of data point in array.
Spectral peak terminal method of adjustment the most according to claim 4, it is characterised in that described spectral peak intermediate point
It is spectral peak summit or spectral peak is turned right a little.
6. there is spectral peak terminal and adjust a chromatographic work station for function, including:
Spectral peak intermediate point searches unit, is used for determining spectral peak intermediate point；
Slope value reversion detector unit, for judging the data point in the data set after described spectral peak intermediate point successively
Slope value whether reversion occurs, if there is reversion, after last data point before reversion or reversion
First data point as spectral peak terminal；
First data point searches unit, and for without there is reversion, in lookup group, the G-bar of data point is exhausted
Value is less than the first data set of predetermined slope threshold value, and selects any data point in described first data set
As the first data point；
It is characterized in that, also include:
Search judging unit, for continuing to search for N continuous the data set after described first data set, it is judged that institute
Whether the absolute value of the G-bar stating N continuous data set is respectively less than predetermined slope threshold value, and described continuously
The most there is not slope reversion in total data point in N number of data set；
First terminal point confirmation unit, under the judged result being, last by described N continuous data set
One data set is as the second data set, using last data point in described second data set as second
Data point, and select the data point that the amplitude between described first data point and described second data point is minimum to make
For spectral peak terminal.
Chromatographic work station the most according to claim 6, it is characterised in that also include, the second terminal confirms
Unit, under no judged result, in the group after searching described first data set, data point is average
Slope absolute value is more than a data set of described predetermined slope threshold value, and using this data set as the second data
Group, selects any data o'clock in described second data set as the second data point；Search described first data
Slope absolute value between point and described second data point is less than all data points of described predetermined slope threshold value,
Data point minimum for wherein amplitude is defined as spectral peak terminal.
Chromatographic work station the most according to claim 6, it is characterised in that in searching judging unit, as
Fruit has the data point in one group of data set in described N continuous data set and slope reversion occurs, should
Group data set is as the second data set, and using the data point of slope reversion in this data set as the second data
Point, and select using data point minimum for the amplitude between the first data point and the second data point as spectral peak eventually
Point.
9. according to the chromatographic work station described in claim 6,7 or 8, it is characterised in that
N=(0.05*60*SR)/L, L=(PW*SR)/15, wherein SR is the sample rate of data, PW
Being the peak width of spectral peak, L is the number of data point in array.
Chromatographic work station the most according to claim 9, it is characterised in that described spectral peak intermediate point is spectral peak
Summit or spectral peak are turned right a little.
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