Methods and devices for autosampling in sample examination systems

Abstract

Apparatuses, systems, and associated methods for autosampling in sample examination systems are described herein. In one aspect, an apparatus can include a needle defining a lumen, the needle configured to receive a sample within the lumen; one or more electrical conductivity sensors configured to receive the sample via the needle and measure electrical conductivity characteristics of the sample: and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity sensors, and cause an action of the apparatus based on the measured characteristics of the sample.

Description

METHODS AND DEVICES FOR AUTOSAMPLING IN SAMPLE EXAMINATION SYSTEMSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This PCT application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 734,400 (titled “Methods and Devices for Autosampling in Sample Examination Systems’") filed December 16, 2024, the contents of which are hereby incorporation by reference in its entirety for any and all purposes.TECHNICAL FIELD

[0002] The present invention relates generally to improved autosamplers, and associated methods, in sample examination systems.BACKGROUND

[0003] Chromatographic techniques such as high-performance liquid chromatography (HPLC) and ion chromatography (IC) are used to determine target analytes in various sample matrices across multiple industries including environmental, food and beverage, pharmaceutical, biopharmaceutical, and industrial markets. The complexity of samples, however, often necessitates manual sample preparation steps such as dilution, preconcentration, and matrix elimination. These steps are often performed manually, are timeconsuming and labor-intensive, and are prone to contamination and loss of target analytes. These and other issues are addressed in the present disclosure.SUMMARY

[0004] Described herein are sample examination autosamplers capable of screening samples. The autosamplers described herein can provide electrical conductivity measurements, and / or pH measurements of a sample, which can be used to determine whether the sample requires further preparation prior to examination, or can be used to verify the identity of the sample. Further, the autosamplers described herein can include a solid phase extraction (SPE) plunger that can perform matrix elimination of the sample. These features can simplify the analysis workflow and increase sample throughput for sample examination system’s processing of target analytes.

[0005] In one aspect, an apparatus for autosampling of a sample examination system can include: a needle defining a lumen, the needle configured to receive a sample within the lumen; one or more electrical conductivity and / or pH sensors configured to receive the sample via the needle and measure electrical conductivity7or pH characteristics of the sample; and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity7and / or pH sensors, and cause an action of the apparatus based on the measured characteristics of the sample. The apparatus of claim 1, wherein the needle defines a proximate end and a distal end, wherein the one or more electrical sensors are disposed along the distal end of the needle.BRIEF DESCRIPTION OF THE DRAWINGS

[0006] For the purpose of illustrating the invention, there is shown in the drawings a form that is presently preferred; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.

[0007] FIG. 1 A depicts an autosampler needle assembly for sample examination systems according to the present disclosure.

[0008] FIG. IB depicts a cross-sectional view of an autosampler needle according to the present disclosure.

[0009] FIG. 2A depicts an autosampler assembly for sample examination systems according to the present disclosure.

[0010] FIG. 2B depicts a cross-sectional view of an autosampler needle according to the present disclosure.

[0011] FIG. 3 depicts an autosampler assembly for sample examination systems according to the present disclosure.

[0012] FIG. 4 depicts an autosampler assembly for sample examination systems according to the present disclosure.

[0013] FIG. 5 depicts an autosampler assembly for sample examination systems according to the present disclosure.

[0014] FIG. 6 depicts an autosampler measurement assembly according to the present disclosure.

[0015] FIG. 7 depicts an autosampler measurement assembly according to the present disclosure.

[0016] FIG. 8 depicts an autosampler measurement assembly according to the present disclosure.

[0017] FIG. 9 depicts an autosampler measurement assembly according to the present disclosure.

[0018] FIG. 10 depicts an autosampler measurement assembly according to the present disclosure.

[0019] FIG. 11 depicts a circuit diagram for an autosampler measurement assembly according to the present disclosure.

[0020] FIG. 12 depicts a conductivity graph according to the present disclosure.

[0021] FIG. 13 depicts an autosampler measurement system according to the present disclosure.

[0022] FIG. 14 depicts sample concentration graphs according to the present disclosure.

[0023] FIG. 15 depicts a process for autosampling according to the present disclosure.

[0024] FIG. 16 depicts a controller according to the present disclosure.DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0025] The present disclosure may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this invention is not limited to the specific devices, methods, applications, conditions or parameters described and / or shown herein, and that the terminology7used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed invention. Also, as used in the specification including the appended claims, the singular forms "a.” "an.” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. The term “plurality ”, as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable, and it should be understood that steps can be performed in any order. Any documents cited herein are incorporated by reference in their entireties for any and all purposes.

[0026] It is to be appreciated that certain features of the invention which are, for clarity7, described herein in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity7, described in the context of a single embodiment, can also be provided separately or in anysubcombination. Further, reference to values stated in ranges include each and every value within that range. In addition, the term '’comprising" should be understood as having its standard, open-ended meaning, but also as encompassing '‘consisting’’ as well. For example, a device that comprises Part A and Part B can include parts in addition to Part A and Part B, but can also be formed only from Part A and Part B.

[0027] Autosampler assemblies for sample examination systems are described herein. The autosamplers described herein can be configured to screen samples of sample examination systems to determine the ionic strength of the samples through electrical conductivity measurements. The autosamplers can include electrical conductivity sensors disposed along portions of the needle, such that the conducti vity sensors can measure the sample when the needle is disposed in the sample, or during the process of drawing the sample. In some cases, the autosampler can also include pH sensors capable of measuring the acidity levels of a given sample. The measurements of the sample can be used to determine the veracity of the sample, or to determine whether the sample requires preparation processes such as dilution or concentration. The conductivity sensors and pH sensors can be used independently or simultaneously.

[0028] The autosampler assembly can also include a controller for automatic implementation of autosampling procedures. For example, the preparation processes can be implemented by the autosampler without user intervention. In other cases, such as where the veracity of sample is incorrect, the autosampler can terminate the autosampling process or generate a notification for a user indicative of the issues associated with the sample. Thus, the autosamplers described herein can automate and simplify sample preparation while performing sample injections for sample examination systems (e.g., HPLC, IC, etc ). The automation of sample preparation steps as part of the sample injection process can save, for example, between 5 to 60 minutes or more per sample, potentially doubling the throughput of the sample examination system. Further, the autosamplers and processes described herein can reduce contamination and loss of target analytes, improve the consistency of reliability of sample preparation, and can lead to improved accuracy and precision of analytical results.

[0029] FIG. 1A shows an autosampler needle assembly 100 according to the present disclosure. The autosampler needle assembly 100 can include a needle 105. The needle can define (e.g., terminate at) a proximal end 110 and a distal end 115. The proximal end 110 can be in fluidic communication with other components of the sample examination system, such as a chromatography column. The distal end 115 can be configured to be inserted into a sample container, such as a sample vial 120. Further, the needle 105 can define an interiorsurface 125 and an exterior surface 130. The interior surface 125 can define a lumen 135. The lumen 135 can be configured to receive a sample (e.g., a liquid sample) through the distal end 115, and through the lumen 135 towards the proximal end 110. The needle 105 can pass the sample, in some cases, further upstream to the respective sample column for further sample analysis.

[0030] The autosampler needle assembly 100 can also include one or more electrical conductivity sensors 140. The electrical conductivity sensors 140 can be configured to measure electrical conductivity characteristics of a given sample. For example. The electrical conductivity sensors 140 can receive (e.g., contact) a sample, and measure electrical conductivity (e.g., in pS / cm) of the sample. In some cases, the electrical conductivity sensors 140 can be configured to measure an electrical current passing through the sample. In some cases, the electrical conductivity sensors 140 can also include an electrical current emitter that emits the electrical current into the sample, where the electrical conductivity7sensors 140 can then measure current received from the sample.

[0031] The electrical conductivity sensors 140 can be disposed along the needle 105 of the needle assembly 100. For example, as shown in FIG. 1A, the electrical conductivity sensors 140 can be disposed along portions of the needle 105. For example, the electrical conductivity7sensors 140 can be disposed approximate to the distal end 115 of the needle 105. This may allow for the electrical conductivity sensors 140 to measure the sample in the case where the needle 105 is positions the distal end 115 within a sample (e.g., prior to drawing the sample through the lumen 135. In some cases the electrical conductivity sensors 140 can be disposed approximate to the proximate end 110. In some cases, the electrical conductivity7sensors 140 can be disposed along a middle region of the needle 105 between the proximate and distal ends 110 and 115. In some cases, the electrical conductivity sensors 140 can be disposed further upstream from the needle 105, for example in a chamber in fluidic communication with the proximate end 110 of the needle 105 (not shown). Thus, in these cases the sample may be draw n into the needle 105, and further transferred into another chamber for measurement.

[0032] In some cases, the electrical conductivity7sensors 140 can be disposed along the interior wall 125 of the needle 105. In some cases, the electrical conductivity sensors 140 can be disposed along the exterior wall 130 of the needle 105. In some cases, the electrical conductivity sensors 140 can be disposed along both the interior and exterior w alls. When the electrical conductivity sensors 140 are disposed along the interior wall 125, the electrical conductivity sensors 140 can further define the lumen 135 of the needle 105. In some cases,the electrical conductivity sensors 140 can form the distal end 115 of the needle 105. The electrical conductivity sensors 140 can be disposed on surfaces of the needle 105. For example the electrical conductivity sensors 140 can be manufactured separately form the needle 105, can be disposed, attached, coupled, etc. to a surface of the needle. In some cases, the electrical conductivity7sensors 140 can be disposed, attached, coupled, etc., through the manufacturing process of the sensor. For example, the electrical conductivity sensors 140 can formed along a given surface through chemical vapor deposition (CVD), epitaxy, physical vapor deposition (PVD), etc. FIG. IB shows a cross-section view of the needle 105 according to the present disclosure.

[0033] FIG. 2A shows another example of the needle assembly 200 according to the present disclosure. The needle assembly 200 can include electrical conductivity sensors 140 disposed along the interior wall 125 of the needle 105 (e.g., as shown in FIG. 2B).

[0034] FIG. 3 shows another example of a needle assembly 300 according to the present disclosure. In the example of the assembly 300, the electrical conductivity7sensors 140 can be disposed apart from the needle 105. For example, the electrical conductivity sensors 140 can be coupled to another piece of hardware of the autosampler assembly proximate to the proximate end 110 of the needle 105. The electrical conductivity sensors 140 can extend, such as in the direction along the length of the needle 105. In some cases, the electrical conductivity sensors 140 can terminate approximate to the distal end 115 of the needle 105 (e.g.. such that the electrical conductivity sensors 140 is in contact with a sample when the distal end 1 15 of the needle contacts the sample). Thus, in some cases, the electrical conductivity7sensors 140 may not physically contact the needle 105.

[0035] FIG. 4 shows another example of a needle assembly 400 according to the present disclosure. The needle assembly 400 can also include one or more pH or electrochemical sensors 405. The pH or electrochemical sensors 405 can be configured to measure pH or redox characteristics of a given sample. For example, the pH or electrochemical sensors 405 can receive (e.g., contact) a sample, and measure acidity7or redox levels (e.g., between 0 and 14) of the sample. In some cases, the pH or electrochemical sensors 405 can be configured to measure an electrical current or voltage passing through the sample. In some cases, the pH or electrochemical sensors 405 can also include an electrical current emitter that emits the electrical current into the sample, where the pH or electrochemical sensors 405 can then measure electrical current or voltage received from the sample.

[0036] The pH or electrochemical sensors 405 can be disposed along the needle 105 of the needle assembly 100. For example, the pH or electrochemical sensors 405 can be disposedalong portions of the needle 105. For example, the pH or electrochemical sensors 405 can be disposed approximate to the distal end 115 of the needle 105. This may allow for the pH or electrochemical sensors 405 to measure the sample in case where the needle 105 is positions the distal end 115 within a sample (e.g., prior to drawing the sample through the lumen 135). In some cases, the pH or electrochemical sensors 405 can be disposed approximate to the proximate end 110. In some cases, the pH or electrochemical sensors 405 can be disposed along a middle region of the needle 105 between the proximate and distal ends 110 and 115.

[0037] In some cases, the pH or electrochemical sensors 405 can be disposed along the interior wall 125 of the needle 105. In some cases, the pH or electrochemical sensors 405 can be disposed along the exterior wall 130 of the needle 105. In some cases, the pH or electrochemical sensors 405 can be disposed along both the interior and exterior walls. When the pH or electrochemical sensors 405 are disposed along the interior wall 125, the pH or electrochemical sensors 405 can further define the lumen 135 of the needle 105. In some cases, pH or electrochemical sensors 405 can form the distal end 115 of the needle 105. The pH or electrochemical sensors 405 can be disposed on surfaces of the needle 105. For example, the pH or electrochemical sensors 405 can be manufactured separately form the needle 105, can be disposed, attached, coupled, etc. to a surface of the needle. In some cases, the pH or electrochemical sensors 405 can be disposed, attached, coupled, etc., through the manufacturing process of the sensor. For example, the pH or electrochemical sensors 405 can formed along a given surface through chemical vapor deposition (CVD), epitaxy, physical vapor deposition (PVD), etc.

[0038] In the example of the assembly 400 of FIG. 4, the pH or electrochemical sensors 405 can be disposed apart from the needle 105. For example, the pH or electrochemical sensors 405 can be coupled to another piece of hardware of the autosampler assembly proximate to the proximate end 110 of the needle 105. The pH or electrochemical sensors 405 can extend, such as in the direction along the length of the needle 105. In some cases, the pH or electrochemical sensors 405 can terminate approximate to the distal end 115 of the needle 105 (e.g., such that the pH or electrochemical sensors 405 is in contact with a sample when the distal end 115 of the needle contacts the sample. Thus, in some cases, the pH or electrochemical sensors 405 may not physically contact the needle 105.

[0039] FIG. 5 shows another example of a needle assembly 500 according to the present disclosure. The needle assembly can include a solid phase extraction (SPE) plunger 505. The SPE plunger 505 can be configured to reposition SPE material 510. such as a SPE disc, through the sample container 120 containing a sample. For example, the SPE plunger 505 canextend (e.g., along the length of the needle 105). The SPE plunger 505 can define a SPE proximate end 515 and a SPE distal end 520. The SPE plunger 505 can be coupled to another component of the autosampler assembly 500 via the SPE proximate end 515. The SPE distal end 520 can be configured to contact the SPE material 510. In some cases, the SPE plunger 505 can be physically separate from the needle 105, such as that shown in FIG. 5. In some cases, the SPE plunger 505 can be coupled to the needle 105, such as via the exterior wall 130.

[0040] In some cases, the SPE plunger 505 can be actuated simultaneously with the needle 105. For example, the needle and the SPE plunger 505 can be actuated by an actuator. In these cases, the SPE distal end 520 can extend distally away from the distal end 115 of the needle 105, such that the distal end 115 of the needle 105 does not contact the SPE material 510 as the needle 105 and SPE plunger 505 actuate dow n through the sample container 120. In other cases, the SPE plunger 505 can be actuated separately from the needle 105, and thus the length of the SPE plunger 505 may be independent of the length or positioning of the needle 105.

[0041] The SPE plunger 505 can, through its actuation, cause the SPE material 510 to actuate from a top portion of the sample container 120 downward (e g., in the transverse direction (T)). The SPE material 510 can be configured to impede the flow of contaminants through the SPE material, while allow the analytes of interest in the sample to flow through. Thus, as the SPE material 510 actuates through the sample container 120, the SPE material 510 can capture contaminants while allowing the needle 105 access to contaminant-free (e g., contaminant-reduced) sample in the sample container 120.

[0042] FIG. 6 shows an autosampling measurement assembly 600 according to the present disclosure. The autosampling measurement assembly 600 can, in some cases, provide for measurements of samples without making direct contact with the sample. For example, the assembly 600 can include one or more electrical conductivity sensors 140. The one or more electrical conductivity sensors 140 can be configured to contact the exterior surface 130 of the needle 105. as described with reference to FIGS. 1 A-5. The one or more electrical conductivity sensors 140 can be configured to measure an electrical current passing through the sample. For example, needle 105 can transfer a portion of the sample either proximally or distally, via the needle lumen. As the portion of the sample passes through the needle 105, the conductivity sensors 140 can measure electrical conductivity values received via the external surface 130 of the needle 105 contactlessly. In some cases, the one or more electrical conductivity sensors 140 can also include an electrical current emitter that emits the electricalcurrent into the sample, where the electrical conductivity sensors 140 can then measure current received from the sample. The assembly 600 can thus provide measurements of sample conductance contactlessly without having direct contact with the sample.

[0043] FIG. 7 shows an example autosampling measurement assembly 700 according to the present disclosure. The autosampling measurement assembly 700 can be an example of the assembly 600 shown in FIG. 6. The assembly 700 can include charge zones 705 and 710, which can be examples of contactless electrical conductivity sensors 140, measuring the conductance of a sample without having direct contact with the sample. Either or both of charge zones 705 and 710 can be configured to contact the external surface 130 of a needle 105. The charge zones 705 and 710 can be disposed along a substrate 715, which can be a printed circuit board (PCB) in some examples. The substrate 715 can also be configured to contact the external surface 130 of aneedle 105. For example, the external surface 130 can include a concentric cross-section. Substrate 715 and charge zones 705 and 710 can be shaped similarly - for example, shaped to include a concentric or curved contact surface - in order to make sufficient contact with the external surface 130. The charge zones 705 and 710 can receive conductivity measurements from the external surface 130 of the needle 105, and can send corresponding electrical signals to other areas of the substrate 715 in some cases. The assembly 700 can also include a tubing clip body 720. The tubing clip body 720 can couple the assembly 700 to the needle 105. In some cases, the tubing clip body 720 can reinforce and support the substrate 715. The assembly 700 can also include a controller board 725. In some cases, the controller board 725 can receive electrical signals from the charge zone 705 and 710, the substrate 715, or a combination thereof. The controller board 725 in some cases can process the electrical signals to determine electrical conductivity data for a corresponding sample. In some cases the controller board 725 can process the electrical signals and transmit them to another computing device (not shown).

[0044] FIG. 8 shows an autosampling measurement assembly 800 according to the present disclosure. The assembly 800 can be an example of the assembly 700 shown in FIG. 7, but with the assembling connected to (or including) a needle 105. In some cases, the needle can comprise poly ether ether ketone (PEEK). In some cases, the needle 105 can be composed of tubing. In some cases, the needle 105 can include an outer diameter of approximately 1 / 16 . In some cases, the needle 105 can define an inner diameter ranging from approximately 0.007” to 0.020”.

[0045] FIG. 9 shows an autosampling measurement assembly 900 according to the present disclosure. Assembly 900 can include a sample tray 905, which can be configured to hold oneor more sample vials 120. The sample tray 905 can include one or more sample vial holders 910, which can be configured to receive a sample vial 120. The sample vial holder 910 can include one or more electrical conductivity sensors 140, which are described in more detail with reference to FIGS. 1A-8. Electrical conductivity sensors 140 can be shaped, disposed, or both, such that the electrical conductivity sensors 140 make contact with sample vial 120 when the vial is inserted into the sample vial holder 910. The electrical conductivity sensors 140 can be configured to measure electrical conductivity values of a sample contained in the sample vial 120, which can be performed without the electrical conductivity sensors 140 making direct physical contact with the sample in the sample vial 120. The sample measurements can also be performed without the use of a needle 105. FIG. 10 shows an autosampling measurement assembly 1000 according to the present disclosure. The assembly 1000 is similar to that shown in FIG. 9, although without use of an autosampling tray 905.

[0046] FIG. 11 shows a circuitry diagram 1100 for an autosampling measurement assembly according to the present disclosure. The circuitry diagram can represent electrical signal flows from a sample to one or more electrical conductivity sensors 140. For example, CPcan be a shunt capacitance between electrodes of the electrical conductivity sensors 104. Cs can be a capacitance between an electrode and fluid, for example with PEEK as a dielectric. Rsampie can be a fluid resistance of the sample between capacitive electrodes. In some cases, the conductance (G) can be represented by: Gceii = j*a>m*CP+ l / (Rs + (2 / (j*a>m*Cs))). This can apply when Gs->inf Gceii -> j*com*CP+ j*C0m*Cs / 2, Gs->0. and Gceii -> j*®m*CP.

[0047] FIG. 12 shows a capacitive cell vs. sample conductivity graph 1200 according to the present disclosure. The graph 1200 provides exemplary experimental results of capacitive measured at lOKHz. FIG. 13 shows an autosampler measurement system 1300 according to the present disclosure. The system 1300 can include an autosampling measurement assembly 1305, which can be an example of assembly 600, 700, 800, 900, or 1000 described with reference to FIGS. 6-10. The assembly 1305 can be in contact with the needle 120 and can measure conductivity measurements for a sample contained in the needle 120. The measurements can be send to a processor, such as processor 1310. The processor 1310 can determine conductivity data for the sample, and can display via display 1315. FIG. 14 shows sample concentration graphs 1400 tested between an autosampling measurement assembly according to the present disclosure (bottom), and an Inuvion™ conductivity detector.

[0048] FIG. 15 shows a process 1500 for autosampling according to the present disclosure. The method can be performed by an autosampler assembly, such as assemblies 100-1000 asdescribed with reference to FIGS. 1-10. In some cases, the process 1500 can be performed by a sample examination system, such as a HLPC or IC system.

[0049] At Step 1505, a needle of an autosampler can receive a sample. The needle can be positioned within a sample container, such as a vial, via an actuator of the autosampler. In some cases, the receiving can include drawing a portion of the sample into a lumen defined by the needle. The receiving can place one or more electrical conductivity sensors in contact with a portion of the sample.

[0050] At Step 1510, one or more electrical conductivity sensors can measure an electrical conductivity characteristic of the sample. The electrical conductivity sensor can receive an electrical current from the sample (e.g., generated by another component of the autosampler). The one or more electrical conductivity sensors can measure the electrical conductivity from the received electrical current.

[0051] At Step 1515, information indicative of the measured characteristics of the sample can be sent. The one or more electrical conductivity sensors can be in electrical communication with other components of the autosampler, or other components of the sample examination system. For example, the one or more electrical conductivity' sensors can be wiredly connected to a controller of the autosampler. The one or more electrical conductivity sensors can send the information via electrical communications.

[0052] At Step 1520, a controller can determine the measured characteristics deviate from a predefined threshold. The predefined threshold can include an electrical conductivity characteristic corresponding to a sample identification (e.g., for a target analyte).

[0053] At Step 1525, an action of the autosampler can be caused based on the measured characteristic. The action can include a termination of a sampling procedure. For example, the sampling procedure can include actuating the needle to be inserted into a sample, drawing a portion of the sample into a lumen of the needle, and transferring the portion of the sample to an examination column of the corresponding sample examination system. In some cases, the action can include a generating of a notification indicative of the deviation. For example, the controller can generate a notification providing details of the deviation (e.g., the sample may require dilution or concentration or matrix elimination, or the sample identity is in question), and send the notification for display to a user. In some cases, the action can include sample modification procedure. The sample modification procedure can include a dilution process or a concentration process or matrix elimination process. The dilution process can include the autosampler (e.g., the needle of the autosampler) injecting additional material into the sample container (e.g., saline). The concentration process can include injecting additionalmaterial (e.g., additional target analyte) into the sample container. The matrix elimination process can involve the use of SPE to remove matrix components of a sample.

[0054] Other sensors such as a pH sensor or electrochemical sensor may be used in place of or in conjunction with the electrical conductivity sensors in the process 600.

[0055] FIG. 16 depicts a controller 1600 according to the present disclosure. The controller 1600 can be an example of the controller discussed with reference to FIGS. 1-6. The controller 1600 can be a computing device such as a microcontroller, general purpose computer (e g., a personal computer or PC), workstation, mainframe computer system, and so forth. The controller 1600 can include a processor device (e.g., a central processing unit or “CPU’') 1602, a memory device 1604, a storage device 1606, a user interface 1608, a system bus 1610, and a communication interface 1612.

[0056] The processor 1602 can be any type of processing device for carrying out instructions, processing data, and so forth.

[0057] The memory7device 1604 can be any ty pe of memory7device including any one or more of random access memory (“RAM”), read-only memory7(“ROM”), Flash memory, Electrically Erasable Programmable Read Only Memory (“EEPROM”), and so forth.

[0058] The storage device 1606 can be any data storage device for reading / writing from / to any removable and / or integrated optical, magnetic, and / or optical-magneto storage medium, and the like (e.g., a hard disk, a compact disc-read-only memory “CD-ROM”, CD- ReWritable CDRW,” Digital Versatile Disc-ROM “DVD-ROM”, DVD-RW, and so forth). The storage device 1606 can also include a control! er / interface for connecting to the system bus 1610. Thus, the memory7device 1604 and the storage device 1606 are suitable for storing data as well as instructions for programmed processes for execution on the processor 1602.

[0059] The user interface 1608 can include a touch screen, control panel, keyboard, keypad, display or any other type of interface, which can be connected to the system bus 1610 through a corresponding input / output device interface / adapter.

[0060] The communication interface 1612 can be adapted and configured to communicate with any type of external device, or with other components of the sample examination system. The communication interface 1612 can further be adapted and configured to communicate with any' system or network, such as one or more computing devices on a local area network (“LAN”), wide area network (“WAN”), the Internet, and so forth. The communication interface 1612 can be connected directly to the sy stem bus 1610 or can be connected through a suitable interface.

[0061] The controller 1600 can, thus, provide for executing processes, by itself and / or in cooperation with one or more additional devices, that can include algorithms for controlling components of the sample examination system in accordance with the present disclosure. The controller 1600 can be programmed or instructed to perform these processes according to any communication protocol and / or programming language on any platform. Thus, the processes can be embodied in data as well as instructions stored in the memory device 1604 and / or storage device 1606, or received at the user interface 1608 and / or communication interface 1612 for execution on the processor 1602.EXEMPLARY EMBODIMENTS

[0062] The following embodiments are exemplary only and do not serve to limit the scope of the present disclosure of the appended claims. It should be understood that any part of any one or more Embodiments can be combined with any part of any other one or more Embodiments.Embodiment 1

[0063] An apparatus for autosampling of a sample examination system, comprising: a needle defining a lumen, the needle configured to receive a sample within the lumen; one or more electrical conductivity sensors configured to receive the sample via the needle and measure electrical conductivity’ characteristics of the sample; and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity sensors, and cause an action of the apparatus based on the measured characteristics of the sample.Embodiment 2

[0064] The apparatus of Embodiment 1. wherein the needle defines a proximate end and a distal end, wherein the one or more electrical sensors are disposed along the distal end of the needle.Embodiment 3

[0065] The apparatus of any of Embodiments 1 and 2, wherein the one or more electrical sensors are disposed in the lumen defined by the needle.Embodiment 4

[0066] The apparatus of any of Embodiments 1-3, wherein the one or more electrical sensors are disposed on, or define, an interior surface of the needle defining the lumen. Embodiment 5

[0067] The apparatus of any of Embodiments 1 -4, further comprising an actuator configured to position a portion of the needle into the sample.Embodiment 6

[0068] The apparatus of any of Embodiments 1-5, wherein the controller is further configured to determine if the measured characteristics deviate from a predefined threshold; and wherein the action comprises any one or more of terminating a sample draw procedure, generating a notification corresponding to the deviation, or initiating a sample modification procedure.Embodiment 7

[0069] The apparatus of any of Embodiments 1 -6, wherein the sample modification procedure comprises a sample dilution procedure or a sample concentration procedure or sample matrix elimination procedure.Embodiment 8

[0070] The apparatus of any of Embodiments 1-7, further comprising one or more pH, and / or electrochemical sensors configured to receive the sample from the needle and to measure pH and / or electrochemical characteristics of the sample.Embodiment 9

[0071] The apparatus of any of Embodiments 1-8, wherein the one or more pH and / or electrochemical sensors are disposed within the lumen of the needle.Embodiment 10

[0072] The apparatus of any of Embodiments 1 -9, further comprising a plunger extending distally away from a distal end of the needle, wherein the plunger is configured to place a solid phase extraction (SPE) element into contact with a sample prior to the needle receiving the sample.Embodiment 11

[0073] A method for autosampling in a sample examination system, the method comprising: receiving, by a needle of an autosampler, a sample, wherein the needle defines a lumen and comprises one or more electrical conductivity sensors; measuring, by the one or more electrical conductivity sensors, an electrical conductivity characteristic of the sample; and sending information indicative of the measured electrical conductivity characteristic of the sample.Embodiment 12

[0074] The method of Embodiment 11, further comprising: receiving, by a controller, the information indicative of the measured electrical conductivity characteristic; and causing an action of the autosampler based on the information of the measured characteristic.Embodiment 13

[0075] The method of any of Embodiments 11 and 12, further comprising: determining, by the controller, whether the measured electrical conductivity characteristic deviates from a predefined threshold, wherein the causing the action is further based on the determined deviationEmbodiment 14

[0076] The method of any of Embodiments 11-13, wherein the action comprises any one or more of termination of a sampling procedure, a generating of a notification indicative of the determined deviation, a sample concentration procedure, or a dilution procedure or a matrix elimination procedure.Embodiment 15

[0077] The method of any of Embodiments 11-14, wherein the needle further comprises one or more pH sensors, and wherein the method further comprises measuring pH and / or electrochemical characteristics of the received sample.Embodiment 16

[0078] An apparatus for autosampling of a sample examination sy stem, comprising: a sample holder configured to contain or transfer a sample; one or more electrical conductivitysensors configured to receive electrical signals from the sample and measure electrical conductivity7characteristics of the sample; and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity sensors, and cause an action of the apparatus based on the measured characteristics of the sample.

[0079] As described elsewhere herein, the apparatus can be configured such that a contactless electrical conductivity sensor does not itself contact the sample. An electrical conductivity sensor can be in electrical communication with the sample holder; this can be accomplished by direct contact between the electrical conductivity sensor and the sample holder, but this is not a requirement, as the electrical conductivity sensor and the sample holder can be in electrical communication via a conductor, such as a wire, solder, and the like. Direct contact can be between the electrical conductivity- sensor and a surface of the sample holder. The surface of the sample holder can be an internal surface, but can also be an external surface, in some instances.Embodiment 17

[0080] The apparatus of Embodiment 16, wherein the sample holder comprises a sample vial or an autosampler needle.Embodiment 18

[0081] The apparatus of any one of Embodiments 1 -17, wherein the one or more electrical conductivity sensors contact an external surface of the sample holder.Embodiment 19

[0082] The apparatus of any one of Embodiments 1 -18, wherein the one or more electrical conductivity sensors do not make direct contact with the sample. A non-limiting example is provided in FIG. 6, in which sensor 140 does not contact the sample.Embodiment 20

[0083] The apparatus of any one of Embodiments 16-19, wherein the controller is further configured to determine if the measured characteristics deviate from a predefined threshold; and wherein the action comprises any one or more of terminating a sample draw procedure, generating a notification corresponding to the deviation, or initiating a sample modification procedure.

Claims

What is Claimed:1 . An apparatus for autosampling of a sample examination system, comprising: a needle defining a lumen, the needle configured to receive a sample within the lumen; one or more electrical conductivity sensors configured to receive the sample via the needle and measure electrical conductivity characteristics of the sample; and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity sensors, and cause an action of the apparatus based on the measured characteristics of the sample.

2. The apparatus of claim 1, wherein the needle defines a proximate end and a distal end, wherein the one or more electrical sensors are disposed along the distal end of the needle.

3. The apparatus of claim 1, wherein the one or more electrical sensors are disposed in the lumen defined by the needle.

4. The apparatus of claim 1, wherein the one or more electrical sensors are disposed on. or define, an interior surface of the needle defining the lumen.

5. The apparatus of any one of claims 1-4, further comprising an actuator configured to position a portion of the needle into the sample.

6. The apparatus of any one of claims 1-4, wherein the controller is further configured to determine if the measured characteristics deviate from a predefined threshold; and wherein the action comprises any one or more of terminating a sample draw procedure, generating a notification corresponding to the deviation, or initiating a sample modification procedure.

7. The apparatus of claim 6, wherein the sample modification procedure comprises a sample dilution procedure or a sample concentration procedure or sample matrix elimination procedure.

8. The apparatus of any one of claims 1-4, further comprising one or more pH and / or electrochemical sensors configured to receive the sample from the needle and to measure pH and / or electrochemical characteristics of the sample.

9. The apparatus of claim 8, wherein the one or more pH and / or electrochemical sensors are disposed within the lumen of the needle.

10. The apparatus of any one of claims 1-4, further comprising a plunger extending distally away from a distal end of the needle, wherein the plunger is configured to place a solid phase extraction (SPE) element into contact with a sample prior to the needle receiving the sample.

11. The apparatus of any one of claims 1-4, further comprising one or more pH sensors, one or more electrochemical sensors, or both, where the one or more electrical conductivity sensors operate independently of or simultaneously with the one or more pH sensors, the one or more electrochemical sensors, or both.

12. A method for autosampling in a sample examination system, the method comprising: receiving, by a needle of an autosampler, a sample, wherein the needle defines a lumen and comprises one or more electrical conductivity sensors; measuring, by the one or more electrical conductivity7sensors, an electrical conductivity characteristic of the sample; and sending information indicative of the measured electrical conductivity characteristic of the sample.

13. The method of claim 12, further comprising: receiving, by a controller, the information indicative of the measured electrical conductivity characteristic; and causing an action of the autosampler based on the information of the measured characteristic.

14. The method of claim 13, further comprising:determining, by the controller, whether the measured electrical conductivity characteristic deviates from a predefined threshold, wherein the causing the action is further based on the determined deviation.

15. The method of claim 13, wherein the action comprises any one or more of termination of a sampling procedure, a generating of a notification indicative of the determined deviation, a sample concentration procedure, or a dilution procedure or a matnx elimination procedure.

16. The method of any one of claims 12-15, wherein the needle further comprises one or more pH sensors, and wherein the method further comprises measunng pH and / or electrochemical characteristics of the received sample.

17. An apparatus for autosampling of a sample examination system, comprising: a sample holder configured to contain or transfer a sample; one or more electrical conductivity sensors configured to receive electrical signals from the sample and measure electrical conductivity characteristics of the sample; and a controller configured to receive information indicative of the measured characteristics of the sample from the one or more electrical conductivity sensors, and cause an action of the apparatus based on the measured characteristics of the sample.

18. The apparatus of claim 17, wherein the sample holder comprises a sample vial or an autosampler needle.

19. The apparatus of any one of claims 17-18, wherein the one or more electrical conductivity sensors contact an external surface of the sample holder.

20. The apparatus of any one of claims 17-18, wherein the one or more electrical conductivity sensors do not make direct contact with the sample.

21. The apparatus of any one of claims 17-18, wherein the controller is further configured to determine if the measured characteristics deviate from a predefined threshold; and wherein the action comprises any one or more of terminating a sample draw procedure, generating a notification corresponding to the deviation, or initiating a sample modification procedure.

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