Chromatographic peak selector

Claim 2

A chromatographic apparatus comprising a column through which a sample mixture may be directed and including material adapted to separate the individual components of the mixture so that they elute from the column in predetermined sequence to be sensed by a detector which produces an output in the form of a peak-type signal responsive to the concentration of the component in the sample mixture; the improvement in said apparatus for identifying the time when a selected component of interest will elute from the column so as to permit making an accurate measurement of the signal produced thereby, comprising: means to introduce into the column a substance to develop in said output a reference peak occurring prior to the peak of interest and having a uniquely distinguishable characteristic, the rates of passage through said column of said substance and said selected component having a predetermined relationship; means to detect said distinguishable characteristic; means to measure the time between a predetermined initial event and the detection of said reference peak; and means responsive to said measured time for computing in accordance with said predetermined relationship a corresponding time when said peak of interest will be developed.

Claim 3

A chromatographic apparatus comprising a column through which a sample mixture may be directed and including material adapted to separate the individual components of the mixture so that they elute from the column in predetermined sequence to be sensed by a detector which produces an output in the form of a peak-type signal responsive to the concentration of the component in the sample mixture; the improvement in said apparatus for identifying the time when a selected component of interest will elute from the column so as to permit making an accurate measurement of the signal produced thereby, comprising: means to introduce into the column a substance to develop in said output a reference peak occurring prior to the peak of interest and having a uniquely distinguishable characteristic, the rates of passage through said column of said substance and said selected component having a predetermined relationship; means to detect said distinguishable characteristic; means to measure the time between a predetermined initial event and the detection of said reference peak; and means responsive to said measured time for computing in accordance with said predetermined relationship a corresponding time when said peak of interest will be developed.

Claim 4

A chromatographic apparatus comprising a column through which a sample mixture may be directed and including material adapted to separate the individual components of the mixture so that they elute from the column in predetermined sequence to be sensed by a detector which produces an output in the form of a peak-type signal responsive to the concentration of the component in the sample mixture; the improvement in said apparatus for identifying the time when a selected component of interest will elute from the column so as to permit making an accurate measurement of the signal produced thereby, comprising: means to introduce into the column a substance to develop in said output a reference peak occurring prior to the peak of interest and having a uniquely distinguishable characteristic, the rates of passage through said column of said substance and said selected component having a predetermined relationship; means to detect said distinguishable characteristic; means to measure the time between a predetermined initial event and the detection of said reference peak; and means responsive to said measured time for computing in accordance with said predetermined relationship a corresponding time when said peak of interest will be developed.

Claim 5

Apparatus as claimed in claim 1, wherein said measuring means comprises an electronic ramp generator adapted to produce a linearly varying sIgnal until said reference peak is detected, whereby the signal level at that time represents the measured time.

Claim 6

Apparatus as claimed in claim 2, wherein said responsive means includes means for reversing said ramp generator so that it ramps back to its initial condition; means for detecting the time when the ramp signal reaches its initial condition and for starting the integration of the peak of interest.

Claim 9

The method of claim 4, wherein the computation of said second time includes the step of multiplying the first time period by a predetermined constant.

Claim 10

The method of claim 4, including the steps of: measuring the width of the reference peak; performing a mathematical operation on said measured width to compute a predicted period of time for the width of the peak of interest; and integrating the signal produced by the component of interest during the computed time period thereof.

Claim 11

A chromatograph apparatus comprising; chromatographic column means adapted for separating components in a sample mixture driven therethrough by a fluid carrier stream including a preselected reference component having a uniquely recognizable elution characteristic upon separation by the column means, the time of appearance of said reference component bearing a predetermined relationship to the time of appearance of a desired mixture component; detecting means for sensing the emergence of components separated by the column means and for producing signals representative thereof; means for recognizing the detected signal representative of the preselected reference component and for producing a timing signal representative of the time for the reference component to pass through the column means; and means effectively controlled by the timing signal and said predetermined relationship for selecting the detected signal of said desired mixture component to be analyzed and for producing a signal corresponding therewith for analysis.

Claim 12

A chromatograph apparatus comprising; chromatographic column means adapted for separating components in a sample mixture driven therethrough by a fluid carrier stream including a preselected reference component having a uniquely recognizable elution characteristic upon separation by the column means, the time of appearance of said reference component bearing a predetermined relationship to the time of appearance of a desired mixture component; detecting means for sensing the emergence of components separated by the column means and for producing signals representative thereof; means for recognizing the detected signal representative of the preselected reference component and for producing a timing signal representative of the time for the reference component to pass through the column means; and means effectively controlled by the timing signal and said predetermined relationship for selecting the detected signal of said desired mixture component to be analyzed and for producing a signal corresponding therewith for analysis.

Claim 13

The apparatus as claimed in claim 7 and further including: means actuated by the timing signal for integrating the mixture component detected signal for a time period related to the timing signal.

Claim 14

The apparatus as claimed in claim 8, wherein the timing signal producing means further includes: means actuated by the detected reference component signal for generating a first pulse signal having a width related to the width of the detected reference component signal; and means for generating a second pulse signal having a width bearing a first preselected ratio to the width of the first pulse and applying the second pulse signal to the integrating means to determine integration of the desired mixture component signal.

Claim 15

The apparatus as claimed in claim 9, wherein the second pulse signal generating means further includes: means for initiating the second pulse signal at a time bearing a preselected ratio to the time for the reference component to pass through the column means.

Claim 16

A chromatographic apparatus comprising: chromatographic column means for separating components in a sample mixture entrained therethrough by a carrier fluid stream; detecting means for sensing components eluting from the column means and for producing electrical peak signals representative thereof; means for introducing a reference fluid into the column means to identify the time when a selected component in the sample mixture will elute from the column, said reference fluid being selected to produce a uniquely recognizable reference peak signal from the detecting means at a time bearing a predetermined relationship to the time of elution of said selected component; means based on said predetermined relationship, and actuated by the reference peak signal, for generating a control signal substantially coincident in time with the elution of the selected component from the column means; and means actuated by the control signal for analyzing the peak of the selected component.

Claim 17

A chromatographic apparatus comprising: chromatographic column means for separating components in a sample mixture entrained therethrough by a carrier fluid stream; detecting means for sensing components eluting from the column means and for producing electrical peak signals representative thereof; means for introducing a reference fluid into the column means to identify the time when a selected component in the sample mixture will elute from the column, said reference fluid being selected to produce a uniquely recognizable reference peak signal from the detecting means at a time bearing a predetermined relationship to the time of elution of said selected component; means based on said predetermined relationship, and actuated by the reference peak signal, for generating a control signal substantially coincident in time with the elution of the selected component from the column means; and means actuated by the control signal for analyzing the peak of the selected component.

Claim 18

The apparatus as claimed in claim 11, wherein the reference fluid introducing means introduces the reference fluid into the carrier fluid to produce a recognizable vacancy reference peak signal from the detecting means representative of the relative vacancy in the sample mixture of the reference fluid in comparison with the carrier fluid.

Claim 21

The method as claimed in claim 13, wherein said signal is produced by integrating an electrical signal representative of the column output.

Claim 28

The method as claimed in claim 17, wherein said preselected relationship is a predetermined ratio between the passage time of the reference component and the time duration between the introduction of said sample and the start time of said subsequent time period.

Claim 29

The method as claimed in claim 18, wherein the selecting step further includes the steps of: measuring the time width of the reference component after passage through the column; and selecting the desired component for analysis for a time period duration bearing a predetermined ratio to the measured time width of the reference component.

Claim 30

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions the amplitudes of which are detected for analysis purposes; the improved method of selecting a particular component for analysis which comprises: controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component to be selected and which has a unique detectable output signal characteristic distinguishing such reference peak from the peak of any other component in the sample, the time of appearance of said reference peak and of said particular component being related by a certain known function; producing a first signal responsive to the detection of said reference peak and indicating the time between said start time and the time of detection of said reference peak; producing a second signal bearing a predetermined relationship to said first signal in accordance with said certain known function to identify the start of a subsequent time period during which the desired component is at the column output; and selecting for analysis the column output signal appearing during the time period identified by said second signal.

Claim 31

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions the amplitudes of which are detected for analysis purposes; the improved method of selecting a particular component for analysis which comprises: controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component to be selected and which has a unique detectable output signal characteristic distinguishing such reference peak from the peak of any other component in the sample, the time of appearance of said reference peak and of said particular component being related by a certain known function; producing a first signal responsive to the detection of said reference peak and indicating the time between said start time and the time of detection of said reference peak; producing a second signal bearing a predetermined relationship to said first signal in accordance with said certain known function to identify the start of a subsequent time period during which the desired component is at the column output; and selecting for analysis the column output signal appearing during the time period identified by said second signal.

Claim 32

For use with chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic; means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal and operable to produce a selection signal identifying on said time scale a subsequent time period the start of which bears a predetermined relationship to the time of detection of said reference peak; and selection means operable by said selection signal to produce an output signal responsive to the output of said column during said subsequent time period.

Claim 33

For use with chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic; means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal and operable to produce a selection signal identifying on said time scale a subsequent time period the start of which bears a predetermined relationship to the time of detection of said reference peak; and selection means operable by said selection signal to produce an output signal responsive to the output of said column during said subsequent time period.

Claim 34

Apparatus as set forth in claim 21, including means for producing a width signal responsive to the width of the reference peak; said computation means including means responsive to said width signal for controlling the duration of said subsequent time period in accordance with a predetermined relationship to said width signal.

Claim 35

For use with on-line chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic while the material is eluting from the column; means under the control of said recognition means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal while said fluid sample continues to elute from said column and operable to produce a selection signal identifying on said time scale a subsequent time period the start of which bears a predetermined relationship to the preceding time of detection of said reference peak; and selection means operable during said subsequent time period to produce an output signal responsive to the output of said column while the component of interest is being detected.

Claim 36

For use with on-line chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic while the material is eluting from the column; means under the control of said recognition means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal while said fluid sample continues to elute from said column and operable to produce a selection signal identifying on said time scale a subsequent time period the start of which bears a predetermined relationship to the preceding time of detection of said reference peak; and selection means operable during said subsequent time period to produce an output signal responsive to the output of said column while the component of interest is being detected.

Claim 37

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions; the improved method of selecting a particular component for analysis which comprises; controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component to be selected, said reference peak having a unique detectable output characteristic distinguishing the reference peak from the peak of any component in the sample and appearing in the column output at a time which is related to the time of appearance of the component to be selected in accordance with a predetermined relationship; producing a first signal responsive to the detection of said reference peak and which serves to indicate the time between said start time and the time of detection of said reference peak; producing a second signal responsive to said first signal and in accordance with said predetermined relationship to identify a subsequent time after which the desired component appears at the column output; and performing in response to said second signal an operation the function of which is related to the appearance of said desired component at the column output.

Claim 38

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions; the improved method of selecting a particular component for analysis which comprises; controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component to be selected, said reference peak having a unique detectable output characteristic distinguishing the reference peak from the peak of any component in the sample and appearing in the column output at a time which is related to the time of appearance of the component to be selected in accordance with a predetermined relationship; producing a first signal responsive to the detection of said reference peak and which serves to indicate the time between said start time and the time of detection of said reference peak; producing a second signal responsive to said first signal and in accordance with said predetermined relationship to identify a subsequent time after which the desired component appears at the column output; and performing in response to said second signal an operation the function of which is related to the appearance of said desired component at the column output.

Claim 39

The method of claim 24 carried out in an on-line chromatographic analysis wherein said first signal is produced when said reference peak is detected and said second signal is produced while portions of the sample subsequent to said reference peak are eluting from the column.

Claim 40

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions; the improved method of selecting a particular component-peak which comprises: controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component peak to be selected and which has a unique detectable output signal characteristic distinguishing such reference peak from the peak of any other component in the sample, the times of appearance of said reference peak and said component peak having a predetermined relationship; producing a first signal responsive to the detection of said reference peak and representative of the time between said start time and the time of detection of said reference peak; producing a second signal responsive to said first signal and in accordance with said predetermined relationship to identify the selected component-peak signal; and performing in response to said second signal an operation related to said desired component.

Claim 41

In chromatographic analysis of a fluid sample wherein the sample is passed through a chromatographic column to produce at the column output time-separated component-peak elutions; the improved method of selecting a particular component-peak which comprises: controlling the input to the column at a start time to produce in the output thereof a reference peak which precedes the component peak to be selected and which has a unique detectable output signal characteristic distinguishing such reference peak from the peak of any other component in the sample, the times of appearance of said reference peak and said component peak having a predetermined relationship; producing a first signal responsive to the detection of said reference peak and representative of the time between said start time and the time of detection of said reference peak; producing a second signal responsive to said first signal and in accordance with said predetermined relationship to identify the selected component-peak signal; and performing in response to said second signal an operation related to said desired component.

Claim 42

The method of claim 26, wherein sAid operation comprises producing a peak signal responsive to the detection of said selected component; zeroizing an integrator at the time of said second signal; and applying said peak signal to said zeroized integrator.

Claim 43

The method of claim 26, including: producing a third signal representative of the time duration of said reference peak; and performing a mathematical operation on said third signal to compute a predicted time period following said start time and during which the desired component will be available for sensing.

Claim 44

The method of claim 28, including the step of integrating the selected component-peak signal throughout said computed time period.

Claim 45

The method of claim 29, including the step of zeroizing an integrator at the time of said second signal; and applying said selected component-peak signal to said zeroized integrator.

Claim 46

For use with chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by another component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic; means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal and operable therewith to produce a selection signal identifying on said time scale the start of a subsequent time period with the start time bearing a predetermined relationship to the time of detection of said reference peak; an integrator under the control of said selection signal and operable to produce an output signal corresponding to the time-integration of the selected component peak; and means responsive to said selection signal for zeroizing said integrator prior to the integration of said selected component peak.

Claim 47

For use with chromatographic apparatus of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale the components of said fluid sample for individual detection by a detecting apparatus; that improvement for automatically selecting a particular component for analysis which comprises: control means to control the input to the column to produce in the output a reference peak preceding the particular component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by another component in the fluid sample; recognition means operable with said detecting apparatus to recognize said unique characteristic; means to produce a first signal indicative of the time of passage through said column of said reference peak; computation means responsive to said first signal and operable therewith to produce a selection signal identifying on said time scale the start of a subsequent time period with the start time bearing a predetermined relationship to the time of detection of said reference peak; an integrator under the control of said selection signal and operable to produce an output signal corresponding to the time-integration of the selected component peak; and means responsive to said selection signal for zeroizing said integrator prior to the integration of said selected component peak.

Claim 48

In chromatographic equipment of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale component peaks of said fluid sample; that improvement for use in selecting a particular component comprising: control apparatus for controlling the input to the column to produce in the output thereof a reference peak preceding the peak of the desired component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample, the times of appearance of said reference peak and the peak desired to be selected being related in accordance with a predetermined function; a detector responsive to the column output and arranged to recognize said unique characteristic; a signal-producing device coupled to said detector to produce a first signal representative of the time of appearance of said reference peak; computation apparatus responsive to the time represented by said first signal and operable to produce in accordance with said predetermined function a selection signal identifying the desired component; and an output element under the control of said selection signal to produce a function related to the appearance of said desired component.

Claim 49

In chromatographic equipment of the type including a column through which a fluid sample is to be passed for the purpose of separating on a time scale component peaks of said fluid sample; that improvement for use in selecting a particular component comprising: control apparatus for controlling the input to the column to produce in the output thereof a reference peak preceding the peak of the desired component to be selected and having a unique characteristic distinguishing such reference peak from the output signal produced by any other component in the fluid sample, the times of appearance of said reference peak and the peak desired to be selected being related in accordance with a predetermined function; a detector responsive to the column output and arranged to recognize said unique characteristic; a signal-producing device coupled to said detector to produce a first signal representative of the time of appearance of said reference peak; computation apparatus responsive to the time represented by said first signal and operable to produce in accordance with said predetermined function a selection signal identifying the desired component; and an output element under the control of said selection signal to produce a function related to the appearance of said desired component.