Gold nanoparticles decorated with oligo(ethylene glycol) thiols: kinetics of colloid aggregation driven by depletion forces.
We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH2)11(OCH2CH2)6OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 A-1, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.
Zhang
Fajun
F
Institut für Angewandte Physik, Universität Tübingen, Auf der Morgenstelle 10, 72076, Tübingen, Germany.
Dressen
Donald G
DG
Skoda
Maximilian W A
MW
Jacobs
Robert M J
RM
Zorn
Stefan
S
Martin
Richard A
RA
Martin
Christopher M
CM
Clark
Graham F
GF
Schreiber
Frank
F
D000818:Animals; D002417:Cattle; D003102:Colloids; D006046:Gold / Q000737:chemistry*; D007700:Kinetics; D053768:Metal Nanoparticles / Q000737:chemistry*; D011092:Polyethylene Glycols / Q000737:chemistry*; D053838:Scattering, Small Angle; D012710:Serum Albumin, Bovine / Q000378:metabolism; D012965:Sodium Chloride / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013997:Time Factors; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
D003102:Colloids; D013438:Sulfhydryl Compounds; D014867:Water; D012710:Serum Albumin, Bovine; D011092:Polyethylene Glycols; D012965:Sodium Chloride; D006046:Gold