15 replies to this topic

[ClarkSims]

Does anyone know what happens if you mix C60 with H2O2, or if you mix a solution with dissolved C60?

Perchance is it as vigorous as this?

[AdamI]

why do u beleave it's soluable in it, it's not water soluble... soo same thing i would think

Edited by AdamI, 07 January 2013 - 12:32 AM.

[ClarkSims]

I am not curious as to whether C60 is soluble in H2O2. I am curious as to whether it immediately catalyzes the reaction of H2O2 into H2O and O2.

In particular, suppose one drops C60 in Olive Oil into H2O2. Will O2 immediately form?

[niner]

I am not curious as to whether C60 is soluble in H2O2. I am curious as to whether it immediately catalyzes the reaction of H2O2 into H2O and O2.

In particular, suppose one drops C60 in Olive Oil into H2O2. Will O2 immediately form?

Good question. It would be pretty easy to do the experiment. My guess is that it won't be a violent reaction, because the peroxide is in the aqueous phase and the c60-oo is in oil, and you know what they say about those... A better test case might be to use a water solution of c60 tris malonate, or a polyhydroxide, or other such water soluble c60. Maybe even some of GVA's HyFn, but I think that if you want it to have a decent chance of working rapidly like bleach does that you'd want a decent concentration of c60. I doubt you'd see much at a nanomolar concentration, even if it was working.

[JohnD60]

bleach is made from a sodium hypochlorite which a highly reactive halogenated compound. I can't image C60 would act in any way similarly when mixed with H2O2

[niner]

Lots of things will make H2O2 fall apart. Manganese dioxide, for example. The mechanism is a redox cycle between Mn2+ and Mn3+, just like in Mn-SOD. I don't know what the mechanism with hypochlorite is, but c60 is certainly good at shuttling electrons around.

[Turnbuckle]

I am not curious as to whether C60 is soluble in H2O2. I am curious as to whether it immediately catalyzes the reaction of H2O2 into H2O and O2.

In particular, suppose one drops C60 in Olive Oil into H2O2. Will O2 immediately form?

No. There is no evident reaction from either C60 dry powder or C60 in oil. Perhaps hydrated C60 would do something.

Edited by Turnbuckle, 07 January 2013 - 03:47 PM.

[ClarkSims]

No. There is no evident reaction from either C60 dry powder or C60 in oil. Perhaps hydrated C60 would do something.

I am stumped. I don't understand how C60 can protect against H2O2.


http://www.ncbi.nlm....pubmed/22642121

Preincubation of cells with 10(-5) M fullerene C60 was shown not only to prevent H2O2--induced AOF generation but to increase viability of H2O2-treated thymocytes at more prolonged time period. The data obtained indicate to fullerene C60 ability to prevent oxidative stress in thymocytes.


On another note, how can C60 protect against CCl4, like in the Baati experiment?

I can play around with chemestry equations and guess:
C60 + H2O + CCl4 ---> C60 + H+ + OH- + CCl3 + Cl-
----> C60- + H+ + Cl- + CCl3OH

Do this 3 more times and you get
3C60- + 4 H+ + 4CL4 + C(OH)4

C(OH)4 is a relatively harmless alcohol (I think)

I am purely speculating here. Does anyone have any insight on how CCl4 is neutralized ?

[ClarkSims]

Here we show that a tris-malonic acid derivative of the fullerene C60 molecule (C3) is capable of removing the biologically important superoxide radical with a rate constant (k(C3)) of 2 x 10(6) mol(-1) s(-1), approximately 100-fold slower than the superoxide dismutases (SOD), a family of enzymes responsible for endogenous dismutation of superoxide. This rate constant is within the range of values reported for several manganese-containing SOD mimetic compounds.
...

We also found that C3 treatment of Sod2(-/-) mice, which lack expression of mitochondrial manganese superoxide dismutase (MnSOD), increased their life span by 300%. These data, coupled with evidence that C3 localizes to mitochondria, suggest that C3 functionally replaces MnSOD, acting as a biologically effective SOD mimetic.

http://www.ncbi.nlm....pubmed/15451059

Well maybe C60 is so good at preventing oxidative damage, because it gets in the membranes of the mitochondria which are producing the O2-, whereas SOD is floating around in the cell cytoplasm?

Edited by ClarkSims, 07 January 2013 - 07:40 PM.

[ClarkSims]

I think I have found the appropriate experimental apparatus to measure 2(H2O2) -> 2(H2O) + O2 catalytic activity.

Catalase activity was assessed using a Clark-type polarographic electrode to measure conversion of hydrogen peroxide to oxygen as described previously (Gonzalez et al., 1995)


http://jpet.aspetjou.../284/1/215.full

[GVA]

I am not curious as to whether C60 is soluble in H2O2. I am curious as to whether it immediately catalyzes the reaction of H2O2 into H2O and O2.

In particular, suppose one drops C60 in Olive Oil into H2O2. Will O2 immediately form?

No. There is no evident reaction from either C60 dry powder or C60 in oil. Perhaps hydrated C60 would do something.

C60HyFn does not react with Í2Î2. The reason of it is that strong water shell of C60HyFn does not allow H2O2 molecule to enter direct contact with surface of C60 molecule.
However if such reaction to carry out in alkaline conditions (pH>9) then C60 molecule is quickly oxidized and breaks up, forming 6 identical products of oxidation (carboxylic acids).

[GVA]

No. There is no evident reaction from either C60 dry powder or C60 in oil. Perhaps hydrated C60 would do something.

I am stumped. I don't understand how C60 can protect against H2O2.


http://www.ncbi.nlm....pubmed/22642121

Preincubation of cells with 10(-5) M fullerene C60 was shown not only to prevent H2O2--induced AOF generation but to increase viability of H2O2-treated thymocytes at more prolonged time period. The data obtained indicate to fullerene C60 ability to prevent oxidative stress in thymocytes.


On another note, how can C60 protect against CCl4, like in the Baati experiment?

I can play around with chemestry equations and guess:
C60 + H2O + CCl4 ---> C60 + H+ + OH- + CCl3 + Cl-
----> C60- + H+ + Cl- + CCl3OH

Do this 3 more times and you get
3C60- + 4 H+ + 4CL4 + C(OH)4

C(OH)4 is a relatively harmless alcohol (I think)

I am purely speculating here. Does anyone have any insight on how CCl4 is neutralized ?

1. FYI: in this work authors used FAS - impure and very poor-quality analogue of C60FWS = water solution of C60HyFn.

2. It is assumed that in hepatocytes (liver cells) CCl4 turns into aggressive CL3COO*-radical. Therefore, in this case, the use of antioxidants is aimed first of all on struggle against such radicals
(e.g. see http://www.pjoes.com...5.3/365-374.pdf).

Edited by GVA, 14 January 2013 - 06:22 PM.

[ClarkSims]

1. FYI: in this work authors used FAS - impure and very poor-quality analogue of C60FWS = water solution of C60HyFn.

2. It is assumed that in hepatocytes (liver cells) CCl4 turns into aggressive CL3COO*-radical. Therefore, in this case, the use of antioxidants is aimed first of all on struggle against such radicals
(e.g. see http://www.pjoes.com...5.3/365-374.pdf).

Thanks for posting that. I am finally getting around to reading the paper. That paper is about 2,4-Dichlorophenoxyacetic Acid, but it mentions in passing:
"The induction of lipid peroxidation in pea microsomes may
be a result of the production of free radicals (e.g. •CCl3,
Cl3CO•, Cl3COO•) formed during metabolism of carbon
tetrachloride in endoplasmatic reticulum with participa-
tion of cytochrome P-450 [46]. Duchnowicz et al. [47, 48]
has shown that 2,4-D caused lipid peroxidation as well as
the increase in membrane fluidity at the 16. carbon atom
of fatty acids and also hemolysis in human erythrocytes."

I am detecting a pattern here. It seems that the body breaks anything down in several steps, and often one of these steps involves something that is a free radical, or which can spontaneously decay into free radicals. It seems that the more common food stuffs, are processed more efficiently, and the unknown xenobiotic chemicals which aren't excreted by the kidney, are processed in a way that creates lots of free radicals.

It seems that even things the body knows, but which doesn't consume in large quantities produce lots of free radicals. For example ethanol is converted to acetaldhyde, which is unstable and can turn into free radicals.

The upshot of this observation, is that strong anti oxidants protect against all sorts of poisoning, and issues with food breakdown.


I get to read Duchnowicz et al. next.

Thanks,

Clark

[ClarkSims]

[1. FYI: in this work authors used FAS - impure and very poor-quality analogue of C60FWS = water solution of C60HyFn.

I just reread the abstract here

http://www.ncbi.nlm....pubmed/22642121

I don't see them mentioning anything about their methods.
Perchance do you have access to the full paper?

[niner]

I am detecting a pattern here. It seems that the body breaks anything down in several steps, and often one of these steps involves something that is a free radical, or which can spontaneously decay into free radicals. It seems that the more common food stuffs, are processed more efficiently, and the unknown xenobiotic chemicals which aren't excreted by the kidney, are processed in a way that creates lots of free radicals.

It seems that even things the body knows, but which doesn't consume in large quantities produce lots of free radicals. For example ethanol is converted to acetaldhyde, which is unstable and can turn into free radicals.

The upshot of this observation, is that strong anti oxidants protect against all sorts of poisoning, and issues with food breakdown.

Yeah, this does happen, though I wouldn't say it's a general rule for xenobiotics. I'd say that the majority of xenobiotics we encounter are metabolized with pretty clean chemistry, but a non-trivial number involve radical intermediates that can make a mess of things.

[GVA]

[1. FYI: in this work authors used FAS - impure and very poor-quality analogue of C60FWS = water solution of C60HyFn.

I just reread the abstract here

http://www.ncbi.nlm....pubmed/22642121

I don't see them mentioning anything about their methods.
Perchance do you have access to the full paper?

Unfortunately, but I have this article in an Ukrainian only. Nevertheless, if you are interested as to reproduce their method, then this article will be useless for you. Descriptions of the method and accurate proofs with what they there work, you will not find in this article. However, in this article there is the reference to some earlier publication in which the method description is given very superficially and vague and in which authors try to reproduce at primitive level our method of production of C60HyFn water solutions (C60FWS). Their solutions they name as C60FAS.
From the scientific point of view, that they have all there is very unscrupulous. For confirmation of my words I give below the reference to article (P. Scharff, … Y.I. Prylutskyy …) with a method which (S.M Hrebinyk,… S.V Prylutska,…) have mentioned in article which you request (http://www.ncbi.nlm.nih.gov/pubmed/22642121).

Referenceis: http://dx.doi.org/10...bon.2003.12.053 (P. Scharff, K. Risch, L. Carta-Abelmann, I.M. Dmytruk, M.M. Bilyi, O.A. Golub, A.V. Khavryuchenko, E.V. Buzaneva, V.L. Aksenov, M.V. Avdeev, Y.I. Prylutskyy, S.S. Durov. StructureofC60 fullereneinwater: spectroscopicdata. Carbon, 42 (2004) 1203–1206) andthat preceded this article, it is possible to see on http://dx.doi.org/10.1039/a907786c (L. Bulavin, I. Adamenko, Yu. Prylutskyy, S. Durov, A. Graja, A. Bogucki, and P. Scharff. Structure of fullerene C60 in aqueous solution. PhysChemChemPhys. 2 (2000) 1627–1629).
If it is necessary, the full texts of these articles I can personally send, on request.


There is something abstract question to all!
If Ñ60, as the antioxidant, interacts with free radicals (e.g. •CCl3, Cl3CO•, Cl3COO•), why Baati at al have not found out any covalent derivatives (adducts) of Ñ60 with such radicals?

Whether such is not strange? Or other molecular mechanisms work there, but which are not connected with direct interaction Ñ60 with free radicals, and all is defined by special properties of water of C60HyFn? (http://www.ipacom.com/index.php/en/fullerenes-and-water-left/75 and http://www.ipacom.com/index.php/en/publications-about-c60hyfn/92 )
SMIE (Sorry for My Imperfect English)!