There are several steps in a successful flash-cooling
experiment:
- Choice of a suitable crystal
- Choice of cryo-protectant
- Solvent exchange
- Choice of the mounting assembly
- Nylon loop construction
- Flash-cooling technique and transfer to the camera
In general, as for almost every crystallographic experiment, crystals should
be of high quality. The experimenter will learn how to define quality for each
crystal system from practical experience. Low quality crystals can be used for
preliminary tests. For some systems, small crystals will freeze better than
large ones and smooth ones better than rough. The absence of cracks is
important as well, as cracks usually widen upon freezing.
When searching for a cryo-protectant (Petsko, 1975; Sutton,
1991), one should first consider the mother liquor composition. For
instance, if the crystal was grown using 2-methyl-2,4-pentanediol (MPD)
as the precipitant, it is most likely ready for freezing without any
additional cryo-protectant. Thus the original mother liquor of any kind
should be the first to be tested (see below). On the other hand,
crystals that grow in salt should be washed in a solution containing a
cryo-protectant, or may need to go through a complete mother liquor
exchange with a cryo-protected solution in order to be cooled to
cryo-temperatures. In general the best choice of cryo-protectant will be
one that most closely resembles the composition of the mother liquor
unless that is mostly salt. If the crystal grows in PEG, then ethylene
glycol, the "monomer" of PEG, would be a good first choice. One may then
try glycerol and even low molecular weight PEG. If the crystal grows in
low MPD concentration, a higher MPD concentration would be the first
option and so on. The nature of the search is trial and error. Some
crystals will be more sensitive to one protectant than to another. A
good place to start the search is with one of the chemicals suggested in
the following list:
- glycerol
- ethylene glycol
- 2-methyl-2,4-pentadiol (MPD)
- dimethyl sulfoxide (DMSO)
- PEG 400
- glucose
- xylitol
- erythritol
- (2R,3R)-(-)-butan 2,3-diol.
Other methods of "cryo-protection" have
been described in Petsko, 1975; Ray et al., 1991; Wierenga et al., 1992.
The most critical portion of the solution in flash-freezing is the part
surrounding the crystal but some cases call for treatment of the interior part
of the solution as well. The basic guidelines are similar to all protein
crystal washes and soaks, but the details will depend on the characteristics of
each case. For most cases a brief dip in a solution of cryo-protectant (wash of
few seconds) will suffice and should be tried first. In other cases a long soak
will be needed. Some crystals will not survive a drastic change in solvent
content, and will have to be taken through a gradual change of the solvent,
either by serial soaks or dialysis. Crystals to which a cryo-protectant cannot
be introduced in their native form might require cross-linking with
glutaraldehyde prior to the introduction of the cryo-protectant. It is also
possible to move the crystal physically from its aqueous environment into oil,
which seals the crystal and minimizes the external excess of solvent (Hope,
1988; Hope et al., 1989).
Before using any crystals, the cryo-protectant should be tested
and the minimal concentration for vitrification must be determined. This
is done following these steps: Construct a loop, approximately 1 x 1mm,
of very thin fishing line (nylon). This loop will be used only to test
the suitability of the mother liquor for flash-cooling, not for data
collection. Starting with the original mother liquor, dip the loop into
the solution and then plunge it rapidly into liquid nitrogen and inspect
the mother liquor drop while still immersed in the liquid nitrogen. If
the frozen drop in the loop turns opaque (milky color) while still
immersed in the liquid nitrogen, the composition of the mother liquor is
not adequate for flash-cooling. Incrementally increase the concentration
of the chosen cryo-protectant and repeat until the frozen drop in the
loop stays clear while still immersed in the liquid nitrogen. It should
be noted that this test usually overestimates the minimal adequate
concentration of cryo-protectant but provides a good starting point.
Once the adequate concentration of the additive is established,
crystals are tested next. Briefly wash an expendable crystal in that
solution and test its diffraction in the X-ray beam. If a brief wash
seems to fail even when the cryo-protectant concentration is set higher,
soak an expendable crystal and look for morphological changes. If none
appear, test the diffraction of soaked crystal. Soaking should be done
in the environment the crystal was grown, i.e. temperature and
atmosphere. The length of soak depends on the temperature and the
viscosity of the mother liquor; at room temperature 4-6 hours, at 4deg.c
the crystal should be left for at least twice as long as for room
temperature. If possible, compare with the mosaicity recorded for
capillary-mount crystals. If the first soaked crystal shows visible
degradation in the cryo-protected solution under the microscope, try to
move the crystal from one solution to another with gradually higher
concentration of the cryo-protectant up to the optimal concentration
(serial soaks), or by means of dialysis (dialysis buttons for
example). If the crystal seems to reject any amount of a specific
cryo-protectant, start over with a different one. Once the
crystal/cryo-protectant passes the visible test but the diffraction
shows an unacceptable increase in mosaicity, try increasing the
protectant concentration. If no improvement is achieved, start over with
another protectant. The final determination of a successful
cryo-protection of a crystal will be made when the diffraction is
assessed. Again, if no other way to introduce a cryo-protectant
succeeds, the crystal may require cross-linking. The process of testing
a cryo-protectant is depicted in the flow-chart below.
The mounting assembly has three parts: the support, the pin and
the base. The term "support" refers to the interface between the crystal
and the pin. The pin is attached to the base and the base is held on the
goniometer head. In the design of the support, on which the crystal is
suspended, one should consider the mechanical stability of the crystal
and the requirement to minimize the size of the drop in which the
crystal is suspended. When conditions allow, the support can be as
simple as a very thin glass rod (Dewan and Tilton, 1987), thinner than
the crystal itself. The crystal can be taken on the tip of the rod. A
touch of vacuum grease applied to the rod's tip will assist in "fishing"
out the crystal. This type of support calls for a tough crystal but when
successful provides a "dry" mount and, in cases where the crystal
extends out of the rod, allows exposure of the crystal to X-rays without
any of the support being in the beam. In the other extreme, a highly
sensitive crystal which is either very thin or soft will not survive
mounting on a rod and will break by mere touch or withdrawal from the
solvent surface. In these cases, a flat glass spatula can be built, and
for the most extreme cases, a "sandwich" spatula can be built to prevent
the surface tension of the drop from breaking the crystal. This method,
although very challenging, is still the only way that allows the
collection of diffraction data from crystals of intact ribosomes and
ribosomal particles (Hope et al., 1989).
This chapter will deal primarily with the most popular and
successful method of crystal support for flash-cooling - the loop (Teng,
1990). The basic knowledge was acquired in different labs, and in
particular, the labs of Dr. P. Sigler of Yale University and
Dr. S. Harrison of Harvard University (especially acknowledging Dr. Greg
van-Düyne and Dr David Rodgers for sharing their practical
experience). Loops are relatively easy to construct, can be made to fit
a specific crystal size, can greatly improve the dexterity of handling
and mounting the crystal, and are suitable to deal with a wide range of
crystal cases. A loop can be made from any thin flexible fiber, but
there are several considerations to be noted. The addition to the
diffraction pattern by loop material must be minimal. Materials such as
some polymers that add rings to the diffraction and metallic loops which
add distinct reflections should be avoided. When searching for loop
material one should test it by exposing the bare loop to the X-ray beam
and observing the result. Loops can be made from fibers of dental floss,
nylon, rayon or silk. The glue with which the fiber's twists are affixed
should also add as little to the diffraction as possible and should be
tested at the same time as the fiber. If the crystal is mechanically
strong, a loop smaller than the crystal will substitute for a glass
rod. In other more common cases the loop should have dimensions that
will accommodate the crystal but minimize the amount of liquid carried
with it in the mounting stage.
The support, as defined above, is suspended on a pin in the
X-ray beam. It is glued to the tip of the pin, which in turn can be
permanently attached to the base. One popular option is depicted in
fig.1.3.
This mounting assembly is made of a steel base and a pin of G22
hypodermic tubing (Small Parts Inc., (305) 557-8222, #HTX-22-36 or any
syringe needle such as TERUMOreg. 22GX). The pin is inserted
through a hole drilled in the base and affixed in place by soldering,
with glue or by friction. Since the base is made of ferromagnetic metal,
it is held on the goniometer head with a piece of adhesive magnetic
strip (fig. 1.4). This assembly is easily put on the goniometer head
with one hand, which facilitates rapid transfers to the camera or other
data collection device.
It is highly recommended to use polyamide nylon 66, 0.025 mm in
diameter, such as is used in eye surgery (Goodfellow Corp.(USA), (800)
821-2870, #AM325710/1). This fiber appears to make a negligible
contribution to the background of the diffraction pattern and is durable
and flexible. The recommended glue is a cyanoacrylate adhesive, also
known as "crazy glue".
- Build a loop-making tool, such as the one shown in figure 1.5, from
transparent material such as perspex, that can be used under a light microscope
(Also see the ultimate loop making machine in fig. 1.7).
- Tack on a short segment of stainless steel wire to a wooden dowel of
approximately 2mm in diameter and bend the tip to a hook (fig. 1.6). The width
of the wire should correlate with the desired width of the final
loop.
- Seal one end of a common disposable glass micropipette with some clay or wax,
or use any glass rod approximately 2mm in diameter and 5cm in length. Cut about
one centimeter of fiber. Apply a touch of crazy glue to the sealed side, fix
both ends of the fiber and let harden.
- Place the hook and the glass capillary face to face in the tool as shown in
fig. 1.6
Now when all is in place the loop is formed, follow the steps depicted in fig.
1.6:
- Hook the loop and start twisting (fig. 1.6a, 1.6b).
- Apply glue all along the twists and as close as possible to the loop. Avoid
fixing the loop to the hook (fig. 1.6c).
- Let the glue harden and snip the loop-stem far from the loop (fig. 1.6d) and
remove carefully from the hook.
To complete the mounting assembly construction, the loop is
glued to the tip of the pin (in the opening of the pin if a hypodermic
tubing is used). This glue must be different from the glue used to affix
the twists of the loop or it will dissolve and the loop will
untwist. The recommended glue to use is crazy glue gel which has
a different solvent than the liquid variety.
| Hypodermic tubing: |
Small Parts Inc., (305) 557-8222 |
#HTX-22-36 |
| Loop fiber: |
Goodfellow Corp.(USA), (800) 821-2870 |
#AM325710/1 |
| Cryo-vials: |
Corning, 2 ml disposable cryogenic vials |
#25724-2 |
| Cryo-storage: |
Nalgene, aluminum cryo-canes |
#5015-0001 |
| Nalgene, PVC cryo-sleeves |
#5016-0001 |
There are three basic methods of flash-cooling:
- Rapid exposure to a low temperature gaseous nitrogen stream at the
camera or other data collection device.
- Plunging the suspended crystal into liquid nitrogen prior to transfer
to the cold gaseous nitrogen stream.
- Plunging the suspended crystal into liquid propane prior to transfer
to the cold gaseous nitrogen stream.
The process must be rapid in all methods in order to ensure the
amorphous solidification of the solvent in and around the crystal and to
allow isotropic freezing of the entire loop contents. It is highly
recommended to run a mock experiment with an empty loop for any camera
configuration and flash-cooling/transfer technique. The loop can hold a
drop of the solution that the crystal is later mounted from. If, at the
end of the transfer, the drop in the loop is anything but "crystal
clear", something is faulty in the transfer process.
Method 1: Exposure to cryo-conditions in the gaseous-liquid interface is less
efficient than in the liquid-liquid interface, but may be sufficient in many
cases. It is advantageous in its simplicity and the fact that further transfers
are unnecessary. Lengthy exposure of the unfrozen crystal to air should be
avoided, or the crystal will degrade or dry out. Position the low temperature
device nozzle in its final position. Block the cold gas stream with a small
piece of cardboard. Mount the crystal and place the mounting assembly on the
goniometer. Rapidly remove the cardboard.
Method 2: This method requires the spindle is either pointing down or has the
ability to be swung to that position. Swing the spindle to a position between
12 and 2 o'clock (unless utilizing a fixed angle spindle pointing down).
Position the low temperature device nozzle slightly further away from its final
position to allow room for the transfer vial. Mount the crystal and plunge it
to a cryo-vial containing liquid nitrogen. Bring the cryo-vial containing the
mounting assembly in liquid nitrogen under the goniometer head and place the
assembly on the magnetic strip. Remove the cryo-vial rapidly and adjust the
position of the nozzle.
Method 3: This method is advantageous over method 2 by providing more
comfortable storage and transfer possibilities but requires use of
flammable materials. Assuming the use of the mounting assembly suggested
above, the appropriate vial to use is the standard 2 ml cryo-vial by
Corning (2 ml disposable cryogenic vials, #25724-2). Propane should be
of high quality to assure solidification at liquid nitrogen
temperature. The propane can be withdrawn in the liquid form or
liquefied in a separate vessel, according to the available propane
source. A small vessel suitable to contain liquid nitrogen should be
fitted with an insert that will hold a few cryo-vials in an upright
position. The rim of the vials should be about 1.5 cm bellow the rim of
the vessel.
- Prepare a cryo-vial full of liquid propane and place the vial in the insert
(the liquid nitrogen level should be close to but bellow the rim of the
cryo-vial).
- Mount the cryo-protected crystal onto the loop and plunge the loop into the
propane. The motion should be rapid in the last 10 cm to avoid having the
crystal experience a gradual change in temperature above the liquid nitrogen
surface. Manual plunging motion is fast enough in most cases but a mechanical
plunger, which requires less dexterity and can be more accurate, is
preferable.
- Fill up the vessel with liquid nitrogen to cover the cryo-vials containing
the mounting assembly and let the propane solidify, typically for 10 minutes.
Another option is to transfer to the aluminum storage cane (see material
sources) and immerse the entire vial in liquid nitrogen.
- When the propane in the cryo-vial containing the mounting assembly is solid,
position the low temperature device nozzle slightly further away from its final
position to allow room for the cryo-vial. While the propane is still solid,
place the vial on the goniometer head. As soon as the propane starts to melt,
remove the cryo-vial. Allow the reminder of the propane to melt while adjusting
the nozzle position. When the propane is all melted, a drop of it might persist
on the loop. It is easy to remove with a thread of filter paper approached up
the cryo stream.
The frozen propane vials can be stored under liquid nitrogen in cryo-storage
aluminum canes (Nalgene, aluminum cryo-canes, #5015-0001) inserted in plastic
sleeves (Nalgene, PVC cryo-sleeves, #5016-0001).
Press here to go to the next section.