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Catalytic generation of nitric oxide...

Cha, Wansik.

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Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors./
Author:	Cha, Wansik.
Description:	191 p.
Notes:	Adviser: Mark E. Meyerhoff.
Contained By:	Dissertation Abstracts International68-02B.
Subject:	Chemistry, Analytical. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3253230

Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors.
Cha, Wansik.

Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors. - 191 p.

Adviser: Mark E. Meyerhoff.

Thesis (Ph.D.)--University of Michigan, 2007.

Novel nitric oxide (NO) generating polymeric materials possessing organoselenium (RSe) catalysts have been developed with the goal of improving the biocompatibility of blood-contacting surfaces in biomedical devices. Low-molecular-weight diselenides were covalently linked to model polymeric materials, e.g., cellulose filter paper and polyethylenimine. Such RSe-derivatized polymers were shown to generate NO from S-nitrosothiols (RSNOs) in the presence of thiol reducing agents (e.g., glutathione). The likely involvement of both immobilized selenol/selenolate and diselenide species for NO liberation from RSNOs is suggested in the proposed catalytic cycle. The new RSe-polymers clearly exhibit the ability to generate NO from RSNO species even after prolonged contact with fresh animal plasma. Such NO generating capability could render RSe-containing polymeric materials more thromboresistant when in contact with flowing blood containing endogenous RSNOs, owing to NO's activity to inhibit platelet adhesion and activation.Subjects--Topical Terms:

586156
Chemistry, Analytical.

Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors.
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005 20110915
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035 $a (UMI)AAI3253230
035 $a AAI3253230
040 $a UMI $c UMI
100 1 $a Cha, Wansik. $3 1291928
245 1 0 $a Catalytic generation of nitric oxide from S-nitrosothiols using organoselenium species and development of amperometric S-nitrosothiol sensors.
300 $a 191 p.
500 $a Adviser: Mark E. Meyerhoff.
500 $a Source: Dissertation Abstracts International, Volume: 68-02, Section: B, page: 0935.
502 $a Thesis (Ph.D.)--University of Michigan, 2007.
520 $a Novel nitric oxide (NO) generating polymeric materials possessing organoselenium (RSe) catalysts have been developed with the goal of improving the biocompatibility of blood-contacting surfaces in biomedical devices. Low-molecular-weight diselenides were covalently linked to model polymeric materials, e.g., cellulose filter paper and polyethylenimine. Such RSe-derivatized polymers were shown to generate NO from S-nitrosothiols (RSNOs) in the presence of thiol reducing agents (e.g., glutathione). The likely involvement of both immobilized selenol/selenolate and diselenide species for NO liberation from RSNOs is suggested in the proposed catalytic cycle. The new RSe-polymers clearly exhibit the ability to generate NO from RSNO species even after prolonged contact with fresh animal plasma. Such NO generating capability could render RSe-containing polymeric materials more thromboresistant when in contact with flowing blood containing endogenous RSNOs, owing to NO's activity to inhibit platelet adhesion and activation.
520 $a Efforts were also undertaken to utilize the new immobilized RSe catalysts to detect RSNO species. To apply a planar-type amperometric NO(g) sensor for directly detecting RSNOs in biological samples (e.g., fresh blood), the NO selectivity was quantitatively examined over both ammonia and nitrite, and compared with other types of amperometric NO sensors. It was found that the NO selectivity coefficient of the planar-type NO sensor can be significantly enhanced up to a thousand fold by treating the porous gas-permeable membrane with a Teflon AFRTM solution. Finally, novel electrochemical devices for the direct detection of RSNO species were developed by modifying the selectivity-improved NO sensor with thin polymeric layers containing immobilized RSe- or copper-based catalysts. Such polymeric layers are capable of decomposing RSNOs to generate NO(g) at the distal tip of the NO sensor. Under optimized conditions, these RSNO sensors were shown to reversibly and quantitatively detect various RSNO species in test solutions down to 0.1 muM concentration. Basic performance parameters (e.g., limit of detection and lifetime, etc.) and factors influencing sensor sensitivity were identified for both the RSe- and copper-based RSNO sensors. The new sensors were shown to be useful in assessing the "NO-generating" ability of fresh blood samples by effectively detecting the total level of reactive RSNO species present in such samples.
590 $a School code: 0127.
650 4 $a Chemistry, Analytical. $3 586156
650 4 $a Chemistry, Polymer. $3 1018428
690 $a 0486
690 $a 0495
710 2 0 $a University of Michigan. $3 777416
773 0 $t Dissertation Abstracts International $g 68-02B.
790 $a 0127
790 1 0 $a Meyerhoff, Mark E., $e advisor
791 $a Ph.D.
792 $a 2007
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3253230