JPH03202753A - Spectrophotometer - Google Patents

Abstract

PURPOSE:To facilitate data processing by storing an arbitrary formula y = f (x1, x2,...xn) in a data processing part when measured data are x1, x2,...xn, substituting the measured data into the formula, and performing operation. CONSTITUTION:When measured data are x1, x2,...xn, an arbitray formula y = f (x1, x2,...xn) is inputted through a keyboard K of a data processing part 2. The inputted formula is stored in a formula memory CM. The measured data which are picked up with a spectrophotometer measuring part 1 are stored in a data memory DM and made to substitute into the formula in the memory CM. Operation is performed, and the result of the data processing is printed out from a printer P. Since the contents of the data processing are made to be the formula and inputted as the formula which is expressed in the normal pattern in this way, the setting of the contents of the data processing becomes easy, and the erroneous setting is eliminated.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a spectrophotometer that can be assembled and executed by a person who analyzes measurement details and data processing methods of measurement results. (Prior Art) Spectrophotometers that can automatically measure the transmittance, absorbance 2 reflectance, etc. of a sample with respect to light of arbitrarily specified wavelengths or a plurality of wavelengths have been conventionally available. A spectrophotometer of this type that has multiple built-in data programs for data processing of measurement results, and allows the user to specify the data processing content and execute the measurement and data processing was also proposed in a patent application filed in 1983. No. 250323 and the like have been proposed. If you want to perform data processing other than the built-in functions of a spectrophotometer equipped with the data processing functions described above, 1
．． Using the output photometric data, the measurer can perform manual calculations or calculator calculations, or use a personal computer to provide a program for desired data processing, transmit the measurement data to that computer, and then perform data processing. A method was used in which the (Question 8 to be solved by the invention) When it becomes necessary to perform data processing other than the built-in functions in a spectrophotometer equipped with several data processing functions, a method of performing calculations by hand or using a calculator. Not only is the calculation of data processing very troublesome, but also the work of creating a report of analysis results that summarizes the processing results and expresses them in tables and graphs is also very difficult, especially when the number of samples is large. The working time is much longer and it is extremely inefficient. When using a personal computer for data processing, there are no problems such as those mentioned above, but there are few people who can create arbitrary data processing programs, and if you ask an expert to create a program, the cost of creating the program will be high and the demands for various analyzes will be high. lack of responsiveness. . Furthermore, even if it is possible to arbitrarily create and run various data processing programs, operations such as creating a calibration curve to determine sample concentration from absorbance, etc., and determining concentration using a calibration curve from measured values are also required. Rather than creating appropriate formulas and substituting measured data into them, these operations are common and frequently used, so it is recommended that spectrophotometer manufacturers create programs for these operations in advance. If the device is equipped with the following information, the ease of use of the device will be improved. Furthermore, in spectroscopic measurements, even if the sample is of the same type, the center wavelength of the absorbance or transmittance peak may shift depending on the acid concentration.
In such a case, using measurement outputs at one or more fixed wavelengths cannot accommodate such wavelength shifts. The present invention is a spectrophotometer that automatically processes data, and is intended to solve the above-mentioned problems by allowing analysts to easily create various data processing programs. Furthermore, it is attempted to automatically cope with the above-mentioned deviation of the peak center wavelength, etc. (Means for solving the problem) Measured data x1, 'x2. . . . Means for inputting an arbitrary mathematical expression y=f (x1, x2.=・xn> as The spectrophotometer is equipped with means for performing calculations according to mathematical formulas and means for displaying the output of the calculation means.In addition, among the calculation processing for the measurement data, the spectrophotometer is capable of creating a calibration curve and calculating the concentration using the calibration curve. Means for performing calculation operations is provided in advance.Furthermore, with these spectrophotometers, one or more wavelength ranges are set in advance, and the maximum or minimum value is detected from the measurement data of these set wavelength ranges. A means is provided, and the maximum value or minimum value thereof is used as the above measurement data x1, x2... The measurement is carried out on the sample, and the measurement results are X1, X2...
・It becomes xn. The data processing is essentially expressed as a function of these measurement results. Once this function is determined, the order and timing of various operations in measurement can be calculated using arithmetic functions. Instructions for operations are sequentially displayed on the display means according to the results, so that the person conducting the analysis can proceed with the analysis operation in accordance with the instructions. Once the measurement data has been collected, the data is processed based on the above formula and output to the display device, so the person performing the analysis can perform the calculations himself or herself.
Frees you from the hassle of creating reports. Data processing can be performed in the form of mathematical formulas in the same way as inputting text, so the effort of creating a specific program can be saved, and no knowledge of programming is required. In addition, the operations of creating a calibration curve and determining the concentration using the calibration curve are extremely common and frequently used, so by providing programs for these operations to the instrument in advance, the operation of the spectrophotometer can be made even easier. It gets easier. Furthermore, as shown in Figure 4, if the peak center wavelength of the spectrum shifts depending on the sample concentration, measuring at a single wavelength λ1 will not detect the peak shift or change in peak height or height, and the two samples will be Although it will be judged that the concentration is the same, if you set the wavelength range from λS to λe and detect the maximum of the measurement output, you can always obtain measurement data with the correct peak center. . (Embodiment) Fig. 1 shows an apparatus according to an embodiment of the present invention. ■ is a spectrophotometer measurement section, 2 is a data processing section.
PU, a keyboard for inputting mathematical formulas, a memory CM for storing inputted mathematical formulas, a data memory DM for storing measurement data, a CRT for displaying inputted mathematical formulas and various instructions, and data processing. It consists of a printer P that prints out the results. Data processing in spectroscopic analysis involves wavelength λ1. Photometric output x at λ2...etc.
1. If you just want to print the photometric output for x2..., etc., the formula to input is yi=xi i=1.2. . λ2. ..., and the absorbance value at each wavelength is set as x1, x2, ... to draw an absorption spectrum. In addition, in cases where the concentration is determined using a calibration curve from the photometric output at a single wavelength, the calibration curve can be expressed mathematically with the concentration as y, and this can be used as a mathematical formula for data processing, for example, y = A. Do it like this: 10B x + CXv'. This is x1, x2. . . . represents a plurality of samples S1, S2 . It is the photometric output at the wavelength λ of... Alternatively, using a plurality of standard samples with known concentrations, the photometric outputs at the wavelength λ are expressed as x1, x2, . ...If you want to create a calibration curve by closing it, the formula for the calibration curve is y=A+I3x+Cx
Let the coefficients A, B, and C of ' be unknown quantities, and use this equation as x1, x2
．． The formula for solving the simultaneous system obtained by substituting any three of ... for A, B, and C is the formula mentioned above. There are various other types of data processing. When one of the three wavelengths, λ1, is the absorption peak wavelength of the sample, and λ2 is the wavelength that gives the baseline outside the peak, and the concentration is determined from the calibration curve, as intermediate variable y1 and concentration y, yl=xl.
-x2 y=A+Byl+c (yl)2 The formula is in the form of two equations. In addition, it may take the form, for example, 1) xi/(λ3-λ1). This formula is used to determine the absorbance proportional to the concentration of the target substance when the absorption peak of the substance to be quantified is on a sloped baseline. The structure of the formula consists of the independent variable (
Measurement output) x1, x2, etc., coefficients, dependent variables, and operation symbols 10. *, /, = and parentheses, curly brackets, square brackets, exponents,
Mathematical expressions such as J, eog, etc. are entered by pressing keys representing these in sequence in the form of the mathematical expression as described above. Specifically, when the operator starts the CPU,
The initial menu will appear, and various operation items will be displayed along with their numbers. Among them, there will be a section called data processing formula settings, so if you press the key with that number on the keyboard, a screen like the one shown in Figure 2 will appear. Displayed on CRT. 1 on this screen
...K6 is a coefficient, the hatched area is a cursor, and 3 can be entered for all coefficients. The cursor can be moved arbitrarily by key operation. A[] below the coefficient. B[], etc., and A, B, etc. are sample identification codes.

By inputting the measurement wavelength in [ ], the independent variable X1 etc. described above is input: For example, if A [3201 is 3201, the 32
It represents the measured output at 0 nm. The code below A[] etc. is an operational code. In FIG. 2, when the cursor is moved to the position after R3= and the number key 2000 is pressed, and the input key is pressed, the screen displays that the coefficient k 3 =2000 has been set as shown in the figure. After entering the coefficients, we begin formulating the formula. For example, first move the cursor to the left parenthesis and press the Select key, then move the cursor to 1 and press the Select key, then move the cursor to Multiplication (*) and press the Select key. , then move the cursor to the sample identification code A[] and press the selection key. (kl*A[] will be displayed in the horizontal frame at the bottom of the screen. Be sure to enter the wavelength data after the sample identification code. Since the program in the CPU is set up so that it can be done manually,
Enter the wavelength value 320 manually using the number keys. To set the wavelength range, enter two wavelength numbers with a comma in between, such as 320.420. Thereafter, numerical formulas as shown are input in the same manner. After entering the formula, 1° measurement will be displayed on the screen, 2. A message saying "Correction" will appear, and when you press the 1 key, measurement will begin, and the CRT will display "Sample A".
and press the measurement start key.'' appears. The operator sets the sample accordingly, and
Press the measurement start key. According to the above formula, the CPU sets the wavelength of the spectrophotometer to 320 nm, imports the measurement output,
Next, move the wavelength to 360 nm and capture the measurement output again, A[320] and A[360] (x1
, x2, etc.) is stored in the data memory. Next, the message ``Please set sample B and press the measurement start key'' is displayed on the CRT screen, and the data of B [2801 is imported in the same manner as above. After that, calculation is performed using the above formula, and the result is displayed together with the measurement data, and the initial message "Please set sample A and press the measurement start key" appears again. Thereafter, measurements are made in the same way for Group A samples and Group B samples (if sample B is a standard sample, it is normal to use the opposite one each time), and the results are displayed on the CRT as shown in the attached table. At the same time, the contents are stored in the data memory DM, and later printed out by the printer P by a print operation. Fig. 3 shows the flow of the above-mentioned operation. The embodiment described above is This method specifies one or more wavelengths to obtain multiple measurement data and performs data processing on them, but depending on the sample, the peak center wavelength of the absorption spectrum may shift depending on the concentration. A wavelength shift at the peak center or local minimum value also appears when a relatively wide peak is on the slope of another large peak.In some cases, the wavelength of the focal point on the spectrum The following example is effective in cases where the wavelength λ1 is fixed as shown in Figure 4. When the centers of the same absorption peak of two samples with different concentrations are shifted, as shown in Figure 4, The height of the peak is judged to be the same for both samples.Therefore, in such a case, predict the shift width of the peak center and scan the wavelength range from λS to λe to find the maximum measurement output for each sample. For example, when determining the mixing ratio of components in a sample by mutual comparison of absorption spectra, it is necessary to calculate the Set the wavelength scanning range to λ1 to λ2, λ3 to λ4, λ5 to λ6.・
..., scan each wavelength range, find the maximum value or minimum value for each range of the measurement output (absorbance in the case of an absorption spectrum), and calculate it as x1, x2 .
...etc. The setting operation in this case is as described above, in A[], set two numbers in [1 separated by a comma, and when finding the minimum, add 0 at the bottom outside of the right parenthesis. If there is this 0 mark, the CPU automatically detects the maximum data between the set wavelengths and sets it as xl, etc. Further, as described in the previous embodiment, the formula is yi=xi i=1.2, . . . n. In the same way, when determining the concentration using a calibration curve or creating a calibration curve using multiple standard samples, you only need to specify one wavelength scanning range, and for that wavelength range, the maximum measurement output of multiple samples is specified. The values are x1, x2.・
...It would be called xn. The apparatus configuration of this embodiment is the same as that of the previous embodiment and is shown in FIG. FIG. 5 shows a flowchart of the operation of the data processing section in this embodiment. First, set various parameters for measurement (a), then set the wavelength range (
mouth). As mentioned above, there may be one wavelength range, or there may be multiple wavelength ranges. After that, the flow of operation is divided into two depending on the measurement mode. The measurement mode is divided into concentration measurement and others, and is specified by the operator. In the case of concentration measurement, the operation proceeds as follows (c). First, regarding the standard sample (b)
Measure in the wavelength range set in (c), and detect the absorbance maximum value or transmittance minimum value from the measurement output of the wavelength rotation described above (
d) and create a calibration curve (e). The method for creating the calibration curve is as described above, but in this example, the program for creating the calibration curve is given to the data processing section in advance.
The operator does not have to enter it himself. Once the calibration curve has been created, measure the sample to be measured in the wavelength range set in (b) (step 3), and check the maximum or minimum output in the above wavelength range (the maximum and minimum are the maximum and minimum at the time of creating the calibration curve,
Detect the concentration (corresponding to the minimum), calculate the concentration using the above calibration curve, perform this operation on all the given samples to be measured, output the measurement results, and end the operation. In the step (g) of calculating the concentration using the calibration curve from the measurement results of the sample to be measured, the calculation program is provided to the data processing section in advance, eliminating the need for the operator to manually perform the calculation. If the measurement mode is other, the operation is from the <mouth) step to the (nu) and <ru) steps.
, (o). In step (nu), measure the wavelength range set in (b) for the sample to be measured, and in step (l), measure the wavelength range set on each side as in step 2). Detects the maximum or minimum of the measured output.The formula in the next step (L) is input arbitrarily by the operator, and in the <L> step, data processing calculations are performed on the measured data according to the formula input by the operator. The operations of (N) to (E) are repeated for all the samples to be measured, and the operation ends when the data processing results are output (S).The above flowchart shows the wavelength range of step (B)
Or multiple wavelengths (d), (g). With the exception of step (l), the first embodiment can be applied as is. (Effect of the invention'4) According to the present invention, the content of data processing can be expressed as a mathematical formula and inputted as the formula normally written.
Setting the data processing content is very easy and there are no mistakes in setting. In actual data processing, the CPU has a built-in program for each unit operation and a program that sequentially selects and connects them according to the given formula, and the CPU uses the above program from the given formula. , data processing programs are constructed and executed, but if a program is created for each new data process, creation errors are inevitable. The present invention, which allows formulas to be entered in the form of formulas, is easy to operate, eliminates input errors, and is suitable for unusual and special measurements.
Analysis requests can be met easily, quickly, and at low cost. In addition, by separating the operations of creating a calibration curve and calculating the concentration using the calibration curve, and providing the operation program to the data processing section in advance, the operator can handle this type of data processing that is frequently used on a daily basis. Operation is conveniently simplified. Furthermore, by setting a wavelength range, detecting the maximum and minimum of the measurement data within the set wavelength range, and using this as data for data processing, correct analysis results can be obtained even if the wavelength of the spectral peak is shifted. It becomes possible to obtain.

[Brief explanation of drawings]

FIG. 1 is a block diagram of an apparatus according to an embodiment of the present invention, FIG. 2 is an illustration of an example of a CRT display screen in the embodiment, FIG. 3 is a flowchart of an example of the operation of the apparatus according to the embodiment, and FIG. 5 is a diagram explaining the necessity of wavelength scanning, and FIG. 5 is a 70-chart of the operation of the data processing section in another embodiment of the present invention. 1... Spectrophotometer measurement section, 2... Data processing section, C
PU... Computer. (See next page) Appendix

Claims (3)

[Claims] (1) Means for inputting an arbitrary formula y=f (x1, x2, ...xn) with measurement data x1, x2, ... xn, means for storing the input formula, and stored formula A spectrophotometer comprising means for substituting collected measurement data into the above-mentioned formula and performing calculations based on the above, and means for outputting the results of the calculations. (2) A means for creating a calibration curve using the measurement data as x1, x2, ...xn, a means for calculating the concentration from the measurement data using the calibration curve, and an arbitrary formula means for inputting =f(x1, x2,... and a spectrophotometer comprising means for outputting the above calculation results. (3) By setting one or more wavelength ranges in advance and scanning each of these wavelength ranges, the maximum or minimum data obtained in each of the wavelength ranges is calculated as x1, x2,...
The spectrophotometer according to claim 1 or 2, wherein xn.