It sounds a bit silly after that nice theoretical discussion, but I would try 
poking the existing oily blobs with a hair.  Since you may be close to xtal 
conditions, stirring up the equilibrium a bit may help nucleate something.  
I've seen this work more than once, although usually with things where we'd 
seen some sign of crystals already.  
Also, try new drops with lower [PEG].
Good luck!
=====================================
Phoebe A. Rice
Dept. of Biochemistry & Molecular Biology
The University of Chicago
phone 773 834 1723
http://bmb.bsd.uchicago.edu/Faculty_and_Research/01_Faculty/01_Faculty_Alphabetically.php?faculty_id=123
http://www.rsc.org/shop/books/2008/9780854042722.asp


---- Original message ----
>Date: Thu, 13 Jan 2011 12:11:54 -0500
>From: CCP4 bulletin board <[email protected]> (on behalf of Edward Snell 
><[email protected]>)
>Subject: Re: [ccp4bb] Phase Separation  
>To: [email protected]
>
>Hi Ruben,
>
>Timing is everything - We are just going through the proofs of a paper 
>entitled "What's in a drop? Correlating observations and outcomes to guide 
>macromolecular crystallization experiments" by Luft, Wolfley and Snell to 
>appear shortly in Crystal Growth and Design. In putting this together we found 
>a number of useful references related to the phase separation phenomena - 
>temperature may be a very useful variable to try. To quote the relative 
>paragraphs and hope we don't start a huge discussion (with references to the 
>figures in the paper removed);
>
>".... There are protein-rich and protein-poor liquid phases. Protein 
>concentrations of 400mg/mL have been measured in the protein-rich phase, a 
>concentration comparable to that found in crystals. (1)  Experimental and 
>theoretical studies demonstrate the formation of immiscible liquid-liquid 
>(L-L) phase separation in the metastable region of the phase diagram forms 
>only where there are short range, and/or highly anisotropic interactions 
>between protein molecules, with further experimental evidence that 
>demonstrates this region is connected with conditions for growing crystals. 
>(2) 
>
>When the temperature of crystallization is near or below the formation 
>temperature of a metastable, immiscible L-L phase separation, at high levels 
>of supersaturation, experimental data and numerical simulations support a 
>two-step, non-classical nucleation process.(2)  In this mechanism a 
>protein-rich liquid phase first forms. Nucleation takes place from this phase 
>followed by initial growth of the nuclei sometimes into the protein-rich and 
>other times into the protein-poor environment. Haas and Drenth(2) suggest that 
>this growth mechanism can lead to fewer crystal defects and more rapid crystal 
>growth as molecules in the concentrated liquid protein phase that surrounds 
>the crystal are not driven to the surface of the crystal by diffusion and 
>therefore misaligned molecules can be more readily exchanged. Literature also 
>supports that it is not the higher protein concentration within the coacervate 
>droplets or the molecular fluidity that may initiate nucleation but rather an 
>interface effect between the dense liquid of high-protein concentration in the 
>droplet and the immiscible surrounding liquid of low-protein concentration.(3) 
>
>When a L-L phase separation is observed ... if one phase is protein-rich and 
>the other protein-poor, then the system is very close to conditions that have 
>the potential to produce crystals. If the protein contains tryptophan 
>residues, then the presence of a protein-rich phase can be verified using UV 
>fluorescence, .... Crystals will sometimes form from the dense liquid phase 
>without intervention; .... As is the case with metastable conditions, this 
>protein-rich immiscible liquid phase can be used for seeding.(4) The other 
>useful and effective option to induce crystal formation is to drive the system 
>towards a higher level of supersaturation, the labile state, using 
>temperature. The rationale for this approach is to increase the attraction 
>between protein molecules by decreasing the temperature.(5) However, this 
>process will be dependent upon the solubility properties of the 
>protein/solvent. Protein solubility is dictated by the combination of the 
>protein and its chemical environment. The same protein can have increased 
>solubility at higher temperatures in one chemical environment, and lower 
>temperatures in a different chemical environment. If the protein/solvent is 
>more soluble at higher temperatures and L-L phase separation is seen in the 
>drop, then decreasing the temperature will drive the system towards a higher 
>level of supersaturation. The opposite applies in cases where the 
>protein/solvent exhibits retro-solubility, i.e. the protein is more soluble at 
>lower temperatures. In this case the experiments would be moved to a higher 
>temperature environment, or set up at a higher temperature in a replicate 
>experiment." 
>
>1.     Kuznetsov, Y. G.; Malkin, A. J.; McPherson, A. Journal of Crystal 
>Growth 2001, 232, 30-39.
>2.     Haas, C.; Drenth, J. Journal of Physical Chemistry B 2000, 104, 368-377.
>3.     Vekilov, P. G. Crystal Growth & Design 2004, 4, 671-685.
>4.     Bergfors, T. J Struct Biol 2003, 142, 66-76.
>5.     Dumetz, A. C.; Chockla, A. M.; Kaler, E. W.; Lenhoff, A. M. Biophys J 
>2008, 94, 570-583.
>
>Hope this helps,
>
>Cheers,
>
>Eddie
>
>
>Edward Snell Ph.D.
>Assistant Prof. Department of Structural Biology, SUNY Buffalo,
>Senior Scientist, Hauptman-Woodward Medical Research Institute
>700 Ellicott Street, Buffalo, NY 14203-1102
>Phone:     (716) 898 8631         Fax: (716) 898 8660 
>Skype:      eddie.snell                 Email: [email protected]  
>Telepathy: 42.2 GHz
>
>Heisenberg was probably here!
>
>From: CCP4 bulletin board [mailto:[email protected]] On Behalf Of Ruben 
>Van der Meeren
>Sent: Thursday, January 13, 2011 4:56 AM
>To: [email protected]
>Subject: [ccp4bb] Phase Separation
>
>Dear all,
>
>I'm trying to crystallize a small, soluble part of a protein (~15kDa, 152AA). 
>I did some standard screens (Crystal Screen I & II + Index screen) with a 
>protein concentration of 25 or 45mg/mL in an 1:1 (0.75µL)96 well set up. In 
>most of the conditions I got phase separation (mostly PEG conditions)! 
>Precipitation was formed in conditions with salt. I did not have phase 
>separation with the control (buffer only, see below). For so far I know my 
>protein was soluble up to a concentration of 60mg/mL (I didn't went higher). 
>Its predicted to have a lot of beta-strands (according to CD-spectra and 
>secondary structure predictions). 
>
>So here are my questions:
>- What is the molecular basis of phase separation? I mean what is going on at 
>molecular level? I would suspect that my protein is not soluble in a PEG 
>environment, is this correct?
>- What can I do to prevent my protein or buffer (?) going into phases? Is it 
>temperature dependent? Are there additives I can add? Do I need to lower the 
>salt concentration? 
>- Are there examples (some of your personal experience) where phase separation 
>was a good thing? 
>
>For your record: the protein is in a 150mM NaCl, 20mM HEPES pH7.5 buffer and 
>the pI is 5-6. It is cloned with a his-tag (but cleaving the his-tag didn't 
>change much). 
>
>Best Regards, 
>Ruben
>
>____________________________________________________________________
>Ruben Van der Meeren
>Ghent University
>L-ProBE, hoogbouw, verdiep 5
>K. L. Ledeganckstraat 35   9000 Ghent (Belgium)
>E-Mail:  [email protected]

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