Dear Horacio,
How does TECEP compare to  BME or DTT? People claim it is better, but I want
some crystallographers' opinion?

Nian

On Sat, Apr 16, 2011 at 4:24 PM, Horacio Botti <[email protected]>wrote:

> Dear Mike
>
> BME readily autooxidizes (need for metal traces and dissolved O2). Is yours
> a metalloprotein? Is your buffer contaminated with metals? Those situations
> would make the case a bit different. If not, unless your BME stock is
> already oxidized, blocking of the accesible thiols with BME should take some
> time. If you treat your protein for 40 min with fresh BME you should not
> observe thiol blocking. If you let the preparation to stay for several days,
> even at 4-6 °C you may observe the blocking that you may be observing.
>
> If you want to prevent Cys blocking you can also change to DTT (it is a
> dithiol, does not readily form mixed disulfides) and use it with caution
> (for thiol reduction it is advisable to use stoichiometric DTT (with respect
> to the number of Cys you need to reduce) and 10 fold excess of BME, look for
> their redox potentials). Take care of not "over-reducing" your protein if
> internal disulfide bonds are expected. Once reduced I suggest you to remove
> any reducing agent and store the protein at -80 °C.
>
> External Cys can be easily oxidized, they are highly expossed to metals and
> oxidants (H2O2, BME disulfides, etc). Diffusion is for sure much faster than
> SS bond formation, although some cys react at almost diffusion-controlled
> rates with oxidants (is yours a thiol'dependen t peroxidase?) You can take a
> look at the following reference (advertising):
>
> 2011. Factors Affecting Protein Thiol Reactivity and Specificity in
> Peroxide Reduction. Chem Res Toxicol.
>
> Metals can contaminate bad quality materials (water, salts, buffers, etc),
> take care of that too. If you need to control the redox state of your
> protein you should use DTNB (Ellman´s reagent), or DTDPy, to measure
> accesible reduced thiol groups.
>
> Good luck!
>
> Horacio
>
>
>
>
> Quoting Kendall Nettles <[email protected]>:
>
>  We see BME adducts in all of our estrogen receptor structures,  though we
>> don't always put them in the models. Sometimes we only see  one or two atoms
>> of the adduct, and in others it is completely  ordered. We only see it on
>> the solvent accessible cysteines. We do  it on purpose. We used to treat the
>> protein with iodoacetic acid to  generate uniform modification of the
>> cysteines, but then we realized  we could get then same homogeneity with
>> 20-50mM BME.
>>
>> Kendall Nettles
>>
>> On Apr 15, 2011, at 4:09 PM, "Michael Thompson" <[email protected]>
>> wrote:
>>
>>  Hi All,
>>>
>>> I was wondering if anyone knew whether or not it is possible for
>>>  reducing agents with thiol groups, such as DTT or  beta-mercaptoethanol
>>> (BME), to form covalent S-S bonds with Cys  residues, particularly
>>> solvent-exposed Cys? I have some puzzling  biochemical results, and in the
>>> absence of a structure (thus far),  I was wondering if this might be
>>> something to try to control for. I  have never heard of this happening (or
>>> seen a structure where there  was density for this type of adduct), but I
>>> can't really think of a  good reason for why this wouldn't happen.
>>> Especially for something  like BME, where the molecule is very much like the
>>> Cys sidechain  and seems to me like it should have similar reactivity. The
>>> only  thing I can think of is if there is a kinetic effect taking place.
>>>  Perhaps the rate of diffusion of these small molecules is much  faster that
>>> the formation of the S-S bond?
>>>
>>> Does anyone know whether or not this is possible, and why it does  or
>>> does not happen?
>>>
>>> Thanks,
>>>
>>> Mike
>>>
>>>
>>>
>>>
>>> --
>>> Michael C. Thompson
>>>
>>> Graduate Student
>>>
>>> Biochemistry & Molecular Biology Division
>>>
>>> Department of Chemistry & Biochemistry
>>>
>>> University of California, Los Angeles
>>>
>>> [email protected]
>>>
>>
>>

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