Siyam M. Ansar

Removal of Molecular Adsorbates on Gold Nanoparticles Using Sodium Borohydride in Water

The mechanism of sodium borohydride removal of organothiols from gold nanoparticles (AuNPs) was studied using an experimental investigation and computational modeling. Organothiols and other AuNP surface adsorbates such as thiophene, adenine, rhodamine, small anions (Br(-) and I(-)), and a polymer (PVP, poly(N-vinylpyrrolidone)) can all be rapidly and completely removed from the AuNP surfaces. A computational study showed that hydride derived from sodium borohydride has a higher binding affinity to AuNPs than organothiols. Thus, it can displace organothiols and all the other adsorbates tested from AuNPs. Sodium borohydride may be used as a hazard-free, general-purpose detergent that should find utility in a variety of AuNP applications including catalysis, biosensing, surface enhanced Raman spectroscopy, and AuNP recycle and reuse.

Ratiometric Surface Enhanced Raman Quantification of Ligand Adsorption onto a Gold Nanoparticle

Surface modification is essential in biomedical applications and nanotechnological developments. We report a novel method using surface-enhanced Raman spectroscopy (SERS) for quantifying ligand adsorption onto gold nanoparticles (AuNPs). After centrifugal or settlement removal of the AuNPs-ligand complex, the amount of unbound ligand in the supernatant was determined ratiometrically with an isotope-encoded SERS reference method where known amounts of isotope-substituted ligand were added to the supernatant as an internal reference. Not only is this ratiometric method robust and accurate but it is also very easy to perform. Using this technique, the binding constant and packing density of the model ligand mercaptobenzimidazole (MBI) on a AuNP was determined for the very first time.

Quantitative Comparison of Raman Activities, SERS Activities, and SERS Enhancement Factors of Organothiols: Implication to Chemical Enhancement

Studying the correlation between the molecular structures of SERS-active analytes and their SERS enhancement factors is important to our fundamental understanding of SERS chemical enhancement. Using a common internal reference method, we quantitatively compared the Raman activities, SERS activities, and SERS enhancement factors for a series of organothiols that differ significantly in their structural characteristics and reported chemical enhancements. We find that while the tested molecules vary tremendously in their normal Raman and SERS activities (by more than 4 orders of magnitude), their SERS enhancement factors are very similar (the largest difference is less than 1 order of magnitude). This result strongly suggests that SERS chemical enhancement factors are not as diverse as initially believed. In addition to shedding critical insight on the SERS phenomena, the common internal reference method developed in this work provides a simple and reliable way for systematic investigation of the correlation between molecular structures and their normal Raman and SERS activities.

Inner Filter Effect on Surface Enhanced Raman Spectroscopic Measurement

Presented herein is a combined experimental and computational study of the gold nanoparticle (AuNP) inner filter effect on surface enhanced Raman spectroscopic (SERS) measurements. Using a bianalyte strategy in which dithiopurine (DTP) and ethanol were employed as the model analytes, we demonstrated that AuNPs enhance DTPs Raman signal but attenuate ethanols Raman intensity. Combined time-resolved UV-vis and Raman measurements showed that AuNP aggregation has significant and an exactly opposite impact on the AuNP inner filter effect and SERS enhancement. This research provides critical new insights regarding SERS signal variation and offers a simple methodology for reliable determination of the SERS enhancement factors.

Comparative Study of the Self-Assembly of Gold and Silver Nanoparticles onto Thiophene Oil

Nanoparticle self-assembly is fundamentally important for bottom-up functional device fabrication. Currently, most nanoparticle self-assembly has been achieved with gold nanoparticles (AuNPs) functionalized with surfactants, polymeric materials, or cross-linkers. Reported herein is a facile synthesis of gold and silver nanoparticle (AgNP) films assembled onto thiophene oil by simply vortex mixing neat thiophene with colloidal AuNPs or AgNPs for ∼1 min. The AuNP film can be made using every type of colloidal AuNPs we have explored, including sodium borohydride-reduced AuNPs with a diameter of ∼5 nm, tannic acid-reduced AuNPs of ∼10 nm diameter, and citrate-reduced AuNPs with particle sizes of ∼13 and ∼30 nm diameter. The AuNP film has excellent stability and it is extremely flexible. It can be stretched, shrunken, and deformed accordingly by changing the volume or shape of the enclosed thiophene oil. However, the AgNP film is unstable, and it can be rapidly discolored and disintegrated into small flakes that float on the thiophene surface. The AuNP and AgNP films prepared in the glass vials can be readily transferred to glass slides and metal substrates for surface-enhanced Raman spectral acquisition.

pH Triggered Recovery and Reuse of Thiolated Poly(acrylic acid) Functionalized Gold Nanoparticles with Applications in Colloidal Catalysis

Thiolated poly(acrylic acid) (PAA-SH) functionalized gold nanoparticles were explored as a colloidal catalyst with potential application as a recoverable catalyst where the PAA provides pH-responsive dispersibility and phase transfer capability between aqueous and organic media. This system demonstrates complete nanoparticle recovery and redispersion over multiple reaction cycles without changes in nanoparticle morphology or reduction in conversion. The catalytic activity (rate constant) was reduced in subsequent reactions when recovery by aggregation was employed, despite unobservable changes in morphology or dispersibility. When colloidal catalyst recovery employed a pH induced phase transfer between two immiscible solvents, the catalytic activity of the recovered nanoparticles was unchanged over four cycles, maintaining the original rate constant and 100% conversion. The ability to recover and reuse colloidal catalysts by aggregation/redispersion and phase transfer methods that occur at low and high pH, respectively, could be used for different gold nanoparticle catalyzed reactions that occur at different pH conditions.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions.