Analytical method and instrument for analysis of liquid sample by liquid chromatography

An analytical method for analyzing a plurality of samples, which is performed by an instrument having an analytical section including, in a flow line, a metering conduit, a precolumn, a first changeover means intermediate said metering conduit and said precolumn for selectively connecting and disconnecting flow between said metering conduit and said precolumn, said first changeover means being connected to a device for providing a carrier liquid to said precolumn through the first changeover means and when said first changeover means is connecting said metering conduit and said precolumn, said carrier liquid being directed through said metering conduit for transferring a mixture in the metering conduit to the precolumn, a separation column and a detector, a second changeover means in said flow line between said precolumn and said separation column for selectively connecting and disconnecting flow between said precolumn and said separation column, said second changeover means being connected to a device for providing eluent to the separation column through the second changeover means and when said second changeover means is connecting said precolumn and said separation column said eluent being directed through the precolumn in order to transfer labeled constituents of the sample which are withdrawn in the precolumn to the separation column and a preparing section including, outside of said flow line, sample containers, a labeling reagent container, a mixing container and a pipette having a pipette nozzle, said analytical method comprising the steps:

• a first step of delivering a sample from any one of the sample containers to the mixing container, delivering a labeling reagent from the labeling reagent container to the mixing container and delivering a mixture of the sample and reagent from the mixture container to an injection port of the flow line to fill the metering conduit of the analytical section with the mixture, each said delivering being performed by actuating the pipette nozzle;
• a second step of transferring the mixture from the metering conduit through the flow line by way of said first changeover means to the precolumn and withdrawing labeled constituents from the mixture in said precolumn;
• a third step of transferring withdrawn labeled constituents from the precolumn through the flow line by way of said second changeover means to the separation column to separate the labeled constituents and detecting the separated labeled constituents with said detector;
• and
• wherein while a first sample is subjected to said first step, a second sample, preceding the first sample, is subjected to said second step and a third sample, preceding the second sample, is subjected to said third step.

An analytical method for analyzing a plurality of samples, which is performed by an instrument having an analytical section including, in a flow line, a metering conduit, a precolumn, a first changeover means intermediate said metering conduit and said precolumn for selectively connecting and disconnecting flow between said metering conduit and said precolumn, said first changeover means being connected to a device for providing a carrier liquid to said precolumn through the first changeover means and when said first changeover means is connecting said metering conduit and said precolumn, said carrier liquid being directed through said metering conduit for transferring a mixture in the metering conduit to the precolumn, a separation column and a detector, a second changeover means in said flow line between said precolumn and said separation column for selectively connecting and disconnecting flow between said precolumn and said separation column, said second changeover means being connected to a device for providing eluent to the separation column through the second changeover means and when said second changeover means is connecting said precolumn and said separation column said eluent being directed through the precolumn in order to transfer labeled constituents of the sample which are withdrawn in the precolumn to the separation column and a preparing section including, outside of the flow line, sample containers, a labeling reagent container, a mixing container and a single pipette having a pipette nozzle, said analytical method comprising the steps:

• a first step of delivering a sample from any one of the sample containers to the mixing container, delivering a labeling reagent from the labeling reagent container to the mixing container and delivering a mixture of the sample and reagent from the mixture container to an injection port of the flow line to fill the metering conduit of the analytical section with the mixture with each delivering step being accomplished by actuating the pipette nozzle;
• a second step of temporarily storing the mixture in said metering conduit and thereafter transferring the mixture temporarily stored in the metering conduit through the flow line by way of said first changeover means to the precolumn and withdrawing labeled constituents from the mixture in said precolumn;
• and
• a third step of transferring withdrawn labeled constituents from the precolumn through the flow line by way of said second changeover means to the separation column to separate the labeled constituents and detecting the separated labeled constituents with said detector;
• and
• wherein while a first sample is subjected to said first step, a second sample preceding the first sample, is subjected to said second step and a third sample, preceding the second sample, is subjected to said third step.

An analytical instrument for analyzing a plurality of samples, the analytical instrument comprising:

• an analytical section including, in a flow line, a conduit, a precolumn, a separation column and a detector;
• a preparing section including, outside of said flow line, sample containers, a labeling reagent container, a mixing container, and delivering means including a pipette having a pipette nozzle, said delivering means delivering a sample from any of the sample containers to the mixing container, delivering a labeling reagent from the labeling reagent container to the mixing container and delivering a mixture of the sample and the reagent from the mixing container to said conduit of the analytical section in said flow line, each delivering operation being accomplished by actuating said pipette nozzle;
• said analytical section further including a first change-over valve in said flow line between said conduit and said precolumn for selectively connecting and disconnecting flow between said conduit and said precolumn, said first changeover valve being connected to a device for providing a carrier liquid to the precolumn through the first changeover valve and, when said first changeover valve is connecting said conduit and said precolumn, said carrier liquid being directed through the conduit for transferring the mixture in the conduit to the precolumn, and a second changeover valve in said flow line between said precolumn and said separation column for selectively connecting and disconnecting flow between said precolumn and said separation column, said second changeover valve being connected to a device for providing an eluent to the separation column through the second changeover valve and, when said second changeover valve is connecting said precolumn and said separation column said eluent being directed through the precolumn in order to transfer labeled constituents of the sample which are withdrawn in the precolumn to the separation column;
• said delivering means, after finishing filling of said conduit with a mixture of a first sample and a labeling reagent from said mixing container, washing said mixing container and delivering a second sample and a labeling reagent to said mixing container with said pipette nozzle and washing said pipette nozzle before filling said conduit with the mixture of the second sample and labeling reagent;
• and wherein
• said instrument further comprises control means for controlling the first and second changeover valves and the delivering means so as to enable a mixing operation of a third sample and labeling reagent subsequent to the mixing of said second sample and labeling reagent in the preparing section, a withdrawal operation for labeled constituents of the second sample in the precolumn, and a separating operation of labeled constituents of the first sample in the separation column to be carried out in parallel or simultaneously, and wherein a liquid used for said labeling reagent, said carrier liquid, and said eluent can be selected for labeling constituents in a sample, for transferring the labeled constituents in said conduit to said precolumn, and for transferring labeled constituents which are withdrawn in said precolumn to said separation column, respectively, independent of one another.

An analytical method by liquid chromatography, said method comprising steps:

• reacting an introduced sample and a reagent in a reaction vessel to form a reaction liquid,
• trapping the reaction liquid in a precolumn to form a trap liquid,
• separating the trap liquid in a separation column, and
• detecting the separated liquid, wherein said method includes
• selectively changing over a sample introduction valve for said reaction liquid between a first state in which said valve is connected to a path for receiving said reaction liquid while said valve is separated from a column changeover valve for liquid, and a second state in which said sample introduction valve is connected to a transfer liquid tank and to said column changeover valve for introducing said received reaction liquid to said column changeover valve,
• selectively changing over said column changeover valve for liquid between a first state in which said column changeover valve is connected to the sample introduction valve for receiving liquid therefrom while said column changeover valve is connected to said precolumn, and a second state in which said column changeover valve is connected to an eluent tank and to said precolumn for introducing trap liquid from said precolumn to said separation column,
• and wherein a next sample and a next reagent are reacted in the reaction vessel after a preceding reaction is completed to form a next reaction liquid, and
• said sample introduction valve is controlled to transfer the next reaction liquid from the reaction vessel to the precolumn to form a next trap liquid, and said
• column changeover valve is controlled to transfer the next trap liquid from the precolumn to said separation column after a preceding separation in the separation column is completed, and
• wherein a liquid to be used for forming said reaction liquid, a liquid stored in said transfer liquid tank and a liquid stored in said eluent tank are selected for use in forming said reaction liquid, for transferring said reaction liquid to said precolumn, and for transferring trap liquid from said precolumn to said separation column, respectively, independent of one another.