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|Title: ||Molecular Modulation Of Material Properties: Studies On Nanoparticles, Nanoassemblies, And Low Molecular-Mass Gelator|
|Authors: ||Srivastava, Aasheesh|
|Advisors: ||Bhattacharya, Santanu|
|Submitted Date: ||Jan-2006|
|Abstract: ||The present thesis titled “Molecular Modulation of Material Properties: Stud-
ies on Nanoparticles, Nanoassemblies and Low Molecular Mass Gelator” deals with the preparation, characterization, and investigations into the properties of gold nanoparticles coated with novel thiols. The coverage of nanoparticle surfaces with these thiols renders them with special characteristics that will be of interest in biological and sensor applications. Also, a novel low molecular mass tetrameric
sugar-based hydrogelator was synthesized and its gelation properties were studied in detail.
Chapter 1 gives a general introduction and an overview about Nanomaterials, with
emphasis towards nanoparticles of gold, which form the basis of this work. It delves
with the history of research in noble metal nanoparticles, their interesting electronic
and optical properties, the present methods of synthesis of high quality nanoparticles
of noble metals, numerous potential applications of these novel materials, as well as the challenges in their real-life applications, and ends with the future outlook of this ﬁeld of research.
Chapter 2 describes the synthesis and characterization of three cationic lipid-like
disulﬁdes whose molecular structures are shown in Fig. 2.1. Gold nanoparticles
capped with these molecules were then synthesized in small size dispersion by a
simple one-phase protocol. These particles exhibited remarkably diﬀerent solubility properties that were dictated by the molecular structure of the capping agent.
The nanoparticles were characterized by a variety of techniques like UV-visible spec-
troscopy, Transmission Electron Microscopy (TEM), proton Nuclear Magnetic Resonance (1H NMR), Fourier Transform Infra-red (FTIR) spectroscopy, and Zeta Potential measurements. These nanoparticles were then examined for their interactions
Figure 1: Chemical Structures of the cationic lipid-like thiols used for nanoparticle preparation
with dipalmitoyl phosphatidyl choline (DPPC) vesicles as model biological membranes. TEM, UV-vis, and Differential Scanning Calorimetry (DSC) were employed to probe the interactions. It was found that the capping agent of the nanoparticle had a strong bearing upon the interactions of the nanoparticles with DPPC vesicles.
Chapter 3 describes the assembly of hydrophilic cationic nanoparticles upon elec-
trostatic interaction with a variety of anionic surfactants. The chemical structures of some of the anions employed in the study, as well as a schematic of cationic nanopar-
ticle are shown in Fig. 2. Upon ion pairing with long-chain anionic surfactants, the
hydrophilic cationic nanoparticles were completely hydrophobized. They could then
be phase-transferred to organic layer. TEM showed that nanoparticles assemble in to a variety of mesostructures upon ion-pairing with anions. The aggregate formation was found to depend critically upon length of the hydrophobic alkyl chain as well as the head-group of the anion. Isothermal Titration Calorimetry (ITC) was employed to probe the interactions of these nanoparticles with anions. It was found that the anions that resulted in nanoparticle precipitation displayed exothermic interactions with the nanoparticle.
Chapter 4 deals with the synthesis of -thiolated metal chelator derivatives whose
structures are shown in Fig. 3. The molecules are based on well-known chelators viz. iminodiacetic acid and bis-(2-pyridylmethyl)amine. While the ﬁrst one is carboxylic acid-based chelator, the second one is pyridine-based. Nanoparticles coated with these chelators were synthesized in a size-controlled manner. These nanoparticles
exhibited pH-controlled reversible assembly. However, while S-IDA based nanoparticles aggregated at low pH values, the S-BPA based nanoparticles aggregated in high pH regimes. Mixed monolayer protected gold nanoparticles were synthesized by employing S-BPA and C12H25SH as capping agents. It resulted in the formation of nanoparticles in low size-dispersion. These nanoparticles were characterized by 1H NMR spectroscopy to infer the ratio of the two capping agents on the nanoparticle surface. These nanoparticles demonstrated metal-ion induced aggregation. It was found that the nanoparticles could differentiate Cu2+ ions from other ions, and immediately formed aggregates in presence of Cu2+ ions.
Chapter 5 describes the synthesis of novel mono-thiolated “Gemini” surfactants for nanoparticle synthesis. Gemini surfactants with different spacers were prepared.
These surfactants had a 12-n-12 kind of molecular structure as shown in the Fig.
4. Upon preparation of nanoparticles with these thiols, the resulting material was
soluble in water in the case of rigid thiols like D2S and DBPS
Chapter 6 deals with the synthesis and hydrogelation properties of a low molecular
mass hydrogelator based on an azobenzene based tetrameric sugar derivative (Fig. 5).
The pKa of carboxylic acids in the molecule were determined using 13C NMR. The
trans-to-cis isomerization of the compound was probed by time-dependent UV-vis studies. The sugar derivative exhibited pronounced hydrogelation capacity, gelling water at micromolar concentration. The gel formed was characterized extensively
Figure 2: Schematic of cationic nanoparticles and molecular structures of the anions employed for nanoparticle assembly
Figure 3: Chemical structures of metal-chelator containing thiols employed for the
pH-controlled and metal-ion mediated nanoparticle assembly
Figure 4: Schematic of cationic nanoparticles and molecular structures of the anions employed for nanoparticle assembly
Figure 5: Chemical Structure of azobenzene-based tetrameric sugar derivative exhibit-
ing pronounced hydrogelation
using melting temperature analysis, UV-vis, FT-IR, circular dichroism spectroscopy
and scanning electron microscopy. The resultant gel exhibited impressive tolerance
to the pH variation of the aqueous phase and gelated water in the pH range of 4 to
10. While UV-vis and CD spectroscopy indicated that pronounced aggregation of the
azobenzene chromophores in the gelator was responsible for gelation, FT-IR studies showed that hydrogen bonding is also a contributing factor in the gelation process.
The melting of gel was found to depend upon the pH of the aqueous medium in which gel was formed. The gel showed considerable photostability to UV irradiation indicating tight intermolecular packing inside gelated state that render azobenzene
groups in the resultant aggregate refractory to photoisomerization. The electron
micrographs of the aqueous gels thus formed showed the existence of spongy globular
aggregates in such gelated materials. Addition of salts to the aqueous medium led to a delay in the gelation process and also caused remarkable morphological changes in
the microstructure of the gel.
Appendix A describes the employment of ligand-free palladium nanoparticles towards eﬃcient catalysis of Heck and Suzuki reactions in aqueous medium. Hexadecyl
trimethylammonium bromide was employed as the surfactant to achieve solubilization of organic compounds in aqueous medium. UV-vis and TEM investigations into the formation of nanoparticles in the reaction media were undertaken. These studies indicate that the nanoparticles were formed by reduction of potassium tetrachloropalladinate by methyl acrylate used as one of the reactants. TEM investigation indicated the formation of nanoparticle assemblies upon solvent drying. Efficient and catalytic synthesis of a number of organic compounds could be achieved in high yield.|
|Appears in Collections:||Organic Chemistry (orgchem)|
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