The interest of researchers in utilizing nanomaterials as carriers for a wide spectrum of molecules has exploded in the last two decades. Nanodiamonds are one class of carbon-based nanomaterials that have emerged as promising drug delivery vehicles and imaging probes. Their ease of functionalization also led to the generation of stimuli-responsive nanodiamonds that deliver drugs on demand in a controlled manner. The ample surface area of NDs allowed for a higher loading of not only small molecules but also macromolecules like genes and proteins. Recently, the unique surface of NDs has attracted more attention as catalyst support in a huge range of organic modification and C-C bond formation reactions. Herein, recent advances in the utilization of nanodiamonds as a drug delivery vehicle and catalytical support are highlighted and summarized to illustrate the potential and versatility of this cheap and commercially available nanomaterial.

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

This research investigates the modification and dispersion and of pristine multiwalled carbon nanotubes (MWCNTs) through a simple solution mixing technique based on noncovalent interactions between poly(phenylene ethynylene)-based conjugated polyelectrolytes functionalized with cationic imidazolium solubilizing groups (PIM-2 and PIM-4) and MWCNTs. Spectroscopic studies demonstrated the ability of PIMs to strongly interact with and efficiently disperse MWCNTs in different solvents, mainly due to π interactions between the PIMs and the MWCNTs. Transmission electron microscopy and atomic force microscopy revealed the coating of the polyelectrolytes on the walls of the nanotubes. Scanning electron microscopy (SEM) studies confirm the homogeneous dispersion of PIM-modified MWCNTs in the poly(methyl methacrylate) (PMMA) matrix. The addition of 1 wt % PIM-modified MWCNTs to the matrix has led to a significant decrease in DC resistivity of the composite (13 orders of magnitude). The increase in electrical conductivity and the improvement in the thermal and mechanical properties of the membranes containing the PIM-modified MWCNTs is ascribed to the formation of MWCNT networks and cross-linking sites that provided channels for the electrons to move in throughout the matrix and reinforced the interface between MWCNTs and PMMA.

We report the synthesis of cadmium-aluminum layered double hydroxide (CdAl LDH) using the reaction-diffusion framework. As the hydroxide anions diffuse into an agar gel matrix containing the mixture of aluminum and cadmium salts at a given ratio, they react to give the LDH. The LDH self-assembles inside the pores of the gel matrix into a unique spherical-porous shaped microstructure. The internal and external morphologies of the particles are studied by electron microscopy and tomography revealing interconnected channels and a high surface area. This material is shown to exhibit a promising performance in the photoreduction of carbon dioxide using solar light. Moreover, the palladium-decorated version shows a significant improvement in its reduction potential at room temperature.

Polyetherimide (PEI) is a widely applied as engineering plastic in the electronics, aerospace, and automotive industries but the disadvantages of extremely low conductivity, atmospheric moisture absorption, and poor fluidity at high temperature limits its application. Herein, commercial multi-walled carbon nanotubes (MWCNTs) were modified with a long alkyl chain molecule, octadecylamine (ODA), to produce a uniform dispersion in commercial PEI matrices. Both covalent and noncovalent modification of MWCNTs with ODA, were prepared and compared. Modified MWCNTs were incorporated in PEI matrices to fabricate nanocomposite membranes by a simple casting method. Investigating mechanical properties, thermal stability, and conductivity of the polyetherimide (PEI)/MWCNT composites showed a unique combination of properties, such as high electrical conductivity, high mechanical properties, and high thermal stability at a low content of 1.0 wt % loading of ODA modified MWCNTs. Moreover, electrical resistivity decreased around 10 orders of magnitude with only 0.5 wt % of modified MWCNTs.

We study the kinetics of intercalation of a fluorescent probe (Rhodamine B (RhB)) during the formation of hierarchal microspheres of Cadmium-Aluminum layered double hydroxide (CdAlA LDH) and its de-intercalation upon transformation from the LDH phase into the cadmium hydroxide β phase (Cd(OH) 2) using a reaction-diffusion framework (RDF) where the hydroxide anions diffuse into an agar gel matrix containing the proper salts-fluorescent probe mixture. In this framework, we achieve the stabilization of the CdAlA LDH, which is known to be thermodynamically unstable and transforms into Cd(OH) 2 and Al(OH) 3 in a short period. RDF is advantageous as it allows with ease the extraction of the co-synthesized polymorphs and their characterization using X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared (FT-IR) and energy dispersive X-ray (EDX). The kinetics of inter/de-intercalation is studied using in situ steady-state fluorescence measurements. The existence of RhB between the LDH layers and its expel during the transition into the β phase are examined via fluorescence microscopy, XRD, and SSNMR. The activation energies of intercalation and de-intercalation of RhB are determined and show dependence on the cationic ratio of the corresponding LDH. We find that the energies of de-intercalation are systematically higher than those of intercalation indicating that the dyes are stabilized due to the probebrucite sheets interactions. SSNMR is used to shed light on the mechanism of intercalation and stabilization of RhB inside the layers of the LDH.

We report the preparation and characterization of three pyrimidine-based monomers, specifically: 1-(2-diallylaminoethyl)uracil, 1-(2-diallylaminoethyl)thymine and 1-(2-diallylaminoethyl)cytosine. Monomer synthesis was initiated by reaction of the pyrimidine with ethylene carbonate to form the hydroxyethyl adduct which was subsequently chlorinated to afford the chloroethyl intermediate. Reaction of the chloroethyl derivatives with diallylamine resulted in the desired monomers. We demonstrated a two-fold increase in the overall yield of the three monomers in comparison to reported procedures. The cyclopolymerization and cyclo-copolymerization of 1-(2-diallylaminoethyl)pyrimidine trifluoroacetate salts in water resulted in low-yield homopolymers. In contrast, the neutral 1-(2-diallylaminoethyl)pyrimidines cyclo-copolymerized with sulfur dioxide and V-50 initiator to yield the corresponding copolymers in higher yields ranging from 30 to 60%.

We report herein the synthesis and characterization of 9-(2-diallylaminoethyl) adenine. We evaluated two different synthetic routes starting with adenine where the optimal route was achieved through coupling of 9-(2-chloroethyl)adenine with diallylamine. The cyclopolymerization and cyclo-copolymerization of 9-(2-diallylaminoethyl)adenine hydrochloride salt resulted in low molecular weight oligomers in low yields. In contrast, 9-(2-diallylaminoethyl)adenine failed to cyclopolymerize, however, it formed a copolymer with SO2 in relatively good yields. The molecular weights of the cyclopolymers were around 1,700–6,000 g/mol, as estimated by SEC. The cyclo-copolymer was stable up to 226 °C. To the best of our knowledge, this is the first example of a free-radical cyclo-copolymerization of a neutral alkyldiallylamine derivative with SO2. These polymers represent a novel class of carbocyclic polynucleotides.