How to run an HPLC (or HPLC 101)

                       High Performance Liquid Chromatography

 

I)                   Making Buffers

II)                 Prepping samples

III)              Turning on HPLC and prepping it

IV)              Troubleshooting

 

I.  Making Buffers

 

Preparing buffers is fairly easy as long as you’re not trying to create a new HPLC

Setup.  Listed here are the two most common buffers used in this laboratory.

Buffer A – Stationary phase

10% Methanol, 0.01% Acetic Acid, pH 5.05

Add 200 ml HPLC grade methanol

Add 2 ml Acetic Acid.

Qs to 2L using HPLC grade water.

Adjust pH to 5.05 using NH4OH.

Degas for 15 minutes.

This buffer will be called buffer A in this protocol.

 

Buffer B – Mobile Phase

100% Methanol

2L of HPLC grade methanol that has been degassed for 15 minutes.

This buffer will be called buffer B in this protocol.

 

II.  Prepping samples          

 

Note: final volume is 180ul MEOH, 120ul 1% acetic acid.

 

     The samples we will generally use on the HPLC come from cell cultures, so the very first thing we will need to do is to centrifuge them (2000 rpm for 10 minutes). 

Then add a known amount of a standard to every sample.  The standard is generally referred to as the internal control.  It should be something that won’t co-elute with the metabolites from the samples.  Normal standard controls used in this lab include: PGB1 and [3H] LTB4.  (3-6 ul) (NET852).

     Save supernatant from each sample by pouring off into separate 50ml tubes.  To the remaining cell debris add 1ml Methanol (f.c. = 10%) and 250 ml of Glacial Acetic Acid.  Vortex and transfer to eppendorf tubes.  Sonicate the eppendorf tubes containing the cell debris for 2 minutes then centrifuge at 14000xg for 10 minutes.  Take that supernatant and add it to the original supernatant.  Dispose of the cell debris in the radioactive waste.

     The final volume varies from sample to sample, but this must remain constant: the final amount of methanol present can not exceed 10%.  For example, with 3 ml of methanol present you would bring up to 30 ml of 1% Acetic Acid.  In all cases, use 1% acetic acid to bring it up to the final volume.  Store on ice until ready to sep-pak.

     The sep-pak cartridges are stored in D438 on the top shelf to your left as you immediately walk into the lab.  The sep-pak box is stored under the hood of the room.

The box should be attached to a waste bottle that is connected to a vacuum pump.  When using this system try not to exceed 200 psi whenever possible.

     Turn on vacuum.  Add 5 ml of methanol and let it wash off.  Add 10 ml 0.5% acetic acid (twice methanol volume) and also let it wash off.  If any methanol is retained on the column still you will lose your entire sample at this point so be sure you wash it well with acetic acid.  Add the samples to each sep-pak cartridge and allow them to wash through (this is the long step and can take up to 2 hours).  When the samples have washed through, add 5ml of 0.5% acetic acid and allow that to wash off.  After this final washing step, turn off the vacuum.

Add labeled 15ml eppendorf tubes under each sep-pak cartridge to collect the next step. Once the tubes are added, add 5 ml of methanol to each cartridge then turn the vacuum on again.  This elution contains all your lipids and fatty acids.

     You can now take the samples and speedvac/dry them.  This normally takes about 4 hours with 5ml of methanol.  Reconstitute the samples in 180ml methanol and 120ml of 1% acetic acid (300ml final volume).

 

III.  Turning on HPLC and prepping it

 

     Turn on the following systems, in this order: both pumps, gradient controller, autosampler, and whichever detectors you plan on using (the UV detector and radiomatic flo-detector are the only 2 detectors connected currently).

     Before you start anything, make sure you have enough buffer to run the HPLC for however long you will need it (generally 4L of buffer B and 2L of buffer A will last for ~80 hours).  The reservoirs are located on the top shelf directly behind the pumps.  In each reservoir should be tubing covered by a frit (metal filter).  The frit should be completely immersed in the buffer.

     On the bottom part of each pump will be a tube covered in plastic.  This is a draw tube and lets you rapidly flush each line without having to use the gradient controller.  On each pump, separately, insert a glass syringe (located next to the pumps), open the draw tube, and pull slowly on the syringe.  This will let you draw out any air bubbles that may be floating in the tubing.  It is imperative that all air bubbles be drawn out; otherwise they will adversely affect your run.  Generally you should draw out a total of 30 ml.

     On the autosampler, click on config page and then scroll down until you get to temp.

Control.  Go ahead and turn that on.  This will commence a cooling procedure, bringing the temperature of the autosampler down to 4oC. 

     Check the ecolume reservoir (behind the flow scintillation analyzer on the top shelf).

If that’s not full, go ahead and fill that up (ecolume can be purchased in the self-service store).  Now, once all that’s done, we’re ready to start.

     The gradient controller has a variety of HPLC methods that we may or may not use.

I’ll briefly list the three most used (which will be more fully explained on a separate

Page:

Gradient 1: The lab’s standard HPLC run.

Gradient 3: Lets us detect Prostaglandins quickly.

Gradient 10: Lets us detect HETE’s quickly.

To start a run, just click on operate gradient then input the correct number.  The timed

Event should always be the same number as the operating gradient.  The timed event is what identifies how long each run should last.

     On the autosampler you can now click autopage.  A page will come out that looks like this:

 

Step     From            To     #     Inj.     Run   

            Vial     Vial  Inj.  Vol.   Time

 

Step just tells you at what part of the setup you’re at.

From Vial is the first vial the autosampler will inject.  The rack inside the autosampler is numbered so it should be pretty easy to figure out where to start.

To vial is the last vial the autosampler will inject.  The rack inside the autosampler is numbered so it should be pretty easy to figure out where to end.

# Inj. is how many times you will inject from one vial.  In almost all cases this will be 1.

Inj. Vol. is how much from each vial you plan on injecting.  The autosampler can not inject a volume greater than 200ml.  Normally, we inject half of every sample when we do our run so, in general, our injection volume is 150ml per run.

Run Time is how long the autosampler will wait before injecting the next sample.

For gradient 1 the run time is set at 115 min.

For gradient 3 the run time is set at 25 min.

For gradient 10 the run time is set at 50 min.

Double check these numbers since the times may vary depending on what you’re supposed to be looking at.

     Now it’s time to use the computer.  You need to click on the detector icon. 

You should get a message that states that it’s connecting to detector.  If you don’t then make sure that the flo-one is turned on.  If you don’t receive the message and the flo-one is on, then you need to go to user->logoff then log back on.  Once you’re connected, you will need to choose the correct method to open:

Method->Open-> here will be listed various files.

                                 E          ICOH3            is for detecting just 3H samples

                                 EICOC14 is for detecting just 14C samples

                                 DUALLAB is for detecting both 3H & 14C

                                 PGELLEN is used for gradient 3

                                 QUIKSOLV is used for gradient 10

Choose the appropriate file you’ll want to use.  You can go back and check the files by

Method->Edit-> then check each part of the file to see if it corresponds with what you want to run.  Once done checking go to Run->Setup then check each portion, including giving a label for your run. Use any system you like as long as it makes sense, but be careful when you store the data and don’t overwrite. Once that’s done you want to click on ok then go back to Run->Update Detector. After that you can click on Run->Start.

     Now you need to add the samples to the autosampler vials.  The vials are small and tend to form air bubbles when you add the samples into them, so be sure you eyeball the vials and flick them if an air bubble does form.  We add half of whatever we have prepared for the HPLC (normally 150ml).

Also run an extra sample that contains the same amount of the internal standard  of the used for the sep-pak elution and a known amount of an expected metabolite for the study (this is known as an external standard). This standard run lets us know the expected elution time of the metabolite of interest, if the system is working properly, and the base number we can use for recovery (For recovery, use the peak area obtained from the standard as 100% recovery.  The peak areas of  the internal standards from the samples should be less, giving you an indication of how much of the sample was lost during the sep-pak elution).

     Ok, everything should be ready to run.  I like to have a hardcopy of everything I’ve done so at this point I generally sit down and write out on a separate sheet of paper what I’m running, the date, the sample identification, and how they will run on the HPLC.

You should then click on the autosampler autopage then start run.  The rest of the system is automated and should run by itself.

 

Be sure that you input more samples than you really need to run in the computer as it only does what the auto sampler sends to it.

Flick vials to remove air bubbles.

Run an extra sample with same amount of the known standard an expected metabolite.

Set auto sampler to 4'C if have many samples.

 

IV.  Troubleshooting

 

1)      Peaks aren’t eluting at the same time?

  Check to make sure you don’t have any air bubbles.  Check the frits and make sure they’re completely immersed in buffer; otherwise they’ll be pumping air  Check the pH and methanol percentage of your buffers.  Failing all that, check for leaks in the system.

2)      Low recovery?

  Check to make sure you didn’t have any methanol retained on the sep-pak.  Also, make sure you added the right amount of internal standard

 

3)      Peak are not there.

  Check to make sure you have the right detection systems on.  3H detector will not spot any 14C labeled sample, no matter how sensitive it is.  Alternatively, check for bubbles in the ecolume line.  Bubbles in this line will do two things.  First it will lower the sensitivity, giving a false low reading.  Second, it will cause 14C samples to bleed heavily into the 3H channel giving false high data in that detection range.