Covalent and non-Covalent Functionalization of Single Walled

1、Covalent and non-Covalent Functionalization of Single Walled Carbon Nanotubes (SWNTs) Paul S. Engel, Vittal B. Gudimetla, David W. Abmayr, Runtang Wang, W.E. Billups, Ravi Singh, and Suzy TortiAs discovered by W. E. Billups and coworkers, SWNT radical anions can react with a variety of organic compo

2、unds to functionalize the SWNT sidewalls. We find that sulfides react as well and can be used to introduce thiol groups onto SWNTs.Maci ntosh PI CTi mage formati s not supportedThiol groups are potentially useful for covalent bonding topolymers, and attaching fluorescent labels and biologicallyactiv

3、e compounds under mild conditions.The evidence for SWNT functionalization is a large increase in the Raman D:G ratio, a sizeable weight loss on TGA and the appearance of “worms of 1.5 to 4.3 nm height in AFM.M a c in to s h P IC Tim a g e fo rm a tis n o t s u p p o rte dMacintosh PICTimage formatis

4、 not supported In contrast to forming chemical bonds to SWNTs, noncovalent functionalization has been used to render SWNTs soluble in water and has the advantage that the fluorescence properties of SWNTs are preserved. However, SWNTs can easily become detached from surfactants like SDBS and poloxome

5、rs like pluronic. A possible solution is to encapsulate SWNTs in a water-soluble polymer from which escape is difficult. This might be achieved by first complexing SWNTs with an appropriate polymer and then crosslinking the backbone.Macintosh PICTimage formatis not supportedThe crosslinking concept

6、is illustrated here. A triblock copolymer is selected consisting of an inner hydrophobic core (gray), a center crosslinkable block (red) and an outer,water-soluble segment (blue). The very hydrophobic SWNT is surrounded by a polystyrene (PS) inner block. The outer block is a hydrophilic polyethylene

7、 glycol (PEG or PEO). The central block is polyacrylic acid (PAA), which is crosslinked by addition of a carbodiimide (EDC) and a water soluble diamine. The resulting species was termed a “PEG-egg by Richard Smalley.PEO(17)-PAA(35)-PS(14) suspending SWNT in waterMacintosh PICTimage formatis not supp

8、ortedMacintosh PICTimage formatis not supportedEDC Diamine crosslinker The black suspension of PEG-eggs (right hand vial above) fluoresces as intensely as SWNTs suspended in SDBS and remains unchanged for years. PEG-eggs can be isolated, lyophilized, and readily re-suspended in water. The aqueous su

9、spension is stable to bovine serum albumin and shows no acute toxicity at 33 ug/mL towards macrophage and kidney cells. 1064 nm NIR irradiation of aqueous PEG-eggs produces a large temperature rise potentially useful for killing cancer cells. concentration (ug/mL)020040060080010001200Temperature increase (oC)05101520253035Temperature of aqueous PEG-eggs after 30 s exposure to a 3W/cm2 YAG laser. Starting temp. was 22 oC.A higher concentration produces a greater temperature rise but multi-walled carbon nanotubes (MWNTs) are very likely to give an even greater response if MWNT PEG-eggs can be