Amphiphilic hyperbranched fluoropolymers as nanoscopic 19F magnetic resonance imaging agent assemblies.
Three hyperbranched fluoropolymers were synthesized and their micelles were constructed as potential (19)F MRI agents. A hyperbranched star-like core was first synthesized via atom transfer radical self-condensing vinyl (co)polymerization (ATR-SCVCP) of 4-chloromethyl styrene (CMS), lauryl acrylate (LA), and 1,1,1-tris(4'-(2''-bromoisobutyryloxy)phenyl)ethane (TBBPE). The polymerization gave a small core with M n of 5.5 kDa with PDI of 1.6, which served as a macroinitiator. Trifluoroethyl methacrylate (TFEMA) and tert-butyl acrylate (tBA) in different ratios were then "grafted" from the core to give three polymers with M(n) of about 120 kDa and PDI values of about 1.6-1.8. After acidolysis of the tert-butyl ester groups, amphiphilic, hyperbranched star-like polymers with M(n) of about 100 kDa were obtained. These structures were subjected to micelle formation in aqueous solution to give micelles having TEM-measured diameters ranging from 3-8 nm and DLS-measured hydrodynamic diameters from 20-30 nm. These micelles gave a narrow, single resonance by (19)F NMR spectroscopy, with a half-width of approximately 130 Hz. The T1/T2 parameters were about 500 and 50 ms, respectively, and were not significantly affected by the composition and sizes of the micelles. (19)F MRI phantom images of these fluorinated micelles were acquired, which demonstrated that these fluorinated micelles maybe useful as novel (19)F MRI agents for a variety of biomedical studies.
Du
Wenjun
W
Department of Chemistry, Washington University in Saint Louis, Saint Louis, Missouri 63130, USA.
Nyström
Andreas M
AM
Zhang
Lei
L
Powell
Kenya T
KT
Li
Yali
Y
Cheng
Chong
C
Wickline
Samuel A
SA
Wooley
Karen L
KL
D000085:Acetates / Q000737:chemistry; D002152:Calorimetry, Differential Scanning / Q000379:methods; D003287:Contrast Media / Q000494:pharmacology; D005462:Fluorine Radioisotopes / Q000737:chemistry*; D007850:Lauric Acids / Q000737:chemistry; D008279:Magnetic Resonance Imaging / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy; D008689:Methacrylates / Q000737:chemistry; D008823:Micelles; D018625:Microscopy, Atomic Force / Q000379:methods; D046529:Microscopy, Electron, Transmission; D008970:Molecular Weight; D054813:Polyhydroxyalkanoates / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D011137:Polystyrenes / Q000737:chemistry; D013499:Surface Properties
D000085:Acetates; D003287:Contrast Media; D005462:Fluorine Radioisotopes; D007850:Lauric Acids; D008689:Methacrylates; D008823:Micelles; D054813:Polyhydroxyalkanoates; D011108:Polymers; D011137:Polystyrenes; C421257:poly(lauryl methacrylate); C426943:poly(p-chloromethylstyrene); C089834:tert-butyl acetate
NMR Biomed. 1996 May;9(3):125-34
8892399
Magn Reson Med. 2007 Oct;58(4):725-34
17899609
Chem Soc Rev. 2006 Jun;35(6):557-71
16729149
Science. 1995 Aug 25;269(5227):1060-1
17755524
Phys Med Biol. 2006 Jan 7;51(1):45-60
16357430
Nano Lett. 2008 Apr;8(4):1131-6
18302330
Circulation. 2002 Nov 26;106(22):2842-7
12451012
Magn Reson Med. 1999 Jan;41(1):80-6
10025614
Adv Drug Deliv Rev. 2001 Apr 25;47(2-3):209-28
11311993
Mol Pharm. 2005 Jul-Aug;2(4):264-72
16053329
Magn Reson Med. 2002 Jan;47(1):82-9
11754446
Chem Soc Rev. 2006 Jun;35(6):512-23
16729145
Adv Drug Deliv Rev. 2005 Jun 15;57(8):1191-209
15935869
Phys Med Biol. 2006 Jan 21;51(2):211-20
16394334
Magn Reson Med. 1994 Jul;32(1):88-97
8084241
Macromolecules. 2007;40(13):4509-4515
18779875
Curr Med Chem. 2005;12(7):819-48
15853714
FASEB J. 2007 Jun;21(8):1647-54
17284484
Curr Top Dev Biol. 2005;70:57-76
16338337
Nat Biotechnol. 2005 Aug;23(8):983-7
16041364
Science. 1995 Aug 25;269(5227):1080-3
17755528
J Am Chem Soc. 2008 Mar 5;130(9):2832-41
18266363
J Cardiovasc Magn Reson. 2007;9(3):565-73
17365236
Adv Drug Deliv Rev. 2000 Mar 15;41(1):55-74
10699305
Magn Reson Med. 2004 Dec;52(6):1255-62
15562481