Identification of Supramolecular Structures of Porphyrin Polymer on Single-Walled Carbon Nanotube Surface Using Microscopic Imaging Techniques.

Although the supramolecular structure of porphyrin polymers on flat surfaces (i.e., mica and HOPG) has been extensively studied, the self-assembly arrays of porphyrin polymers on the SWNT (as curved nanocarbon surfaces) have yet to be fully identified and/or investigated, especially using microscopic imaging techniques, i.e., scanning tunneling microscopy (STM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). This study reports the identification of the supramolecular structure of poly-[5,15-bis-(3,5-isopentoxyphenyl)-10,20-bis ethynylporphyrinato]-zinc (II) on the SWNT surface using mainly AFM and HR-TEM microscopic imaging techniques. After synthesizing around >900 mer of porphyrin polymer (via Glaser-Hay coupling); the as-prepared porphyrin polymer is then non-covalently adsorbed on SWNT surface. Afterward, the resultant porphyrin/SWNT nanocomposite is then anchored with gold nanoparticles (AuNPs), which are used as a marker, via coordination bonding to produce a porphyrin polymer/AuNPs/SWNT hybrid. The polymer, AuNPs, nanocomposite, and/or nanohybrid are characterized using 1H-NMR, mass spectrometry, UV-visible spectroscopy, AFM, as well as HR-TEM measuring techniques. The self-assembly arrays of porphyrin polymers moieties (marked with AuNPs) prefer to form a coplanar well-ordered, regular, repeated array (rather than wrapping) between neighboring molecules along the polymer chain on the tube surface. This will help with further understanding, designing, and fabricating novel supramolecular architectonics of porphyrin/SWNT-based devices.

Synthesis and applicability of reduced graphene oxide/porphyrin nanocomposite as photocatalyst for waste water treatment and medical applications.

This study presents the synthesis and doping of reduced graphene oxide (rGO) with synthesized porphyrin (5,15-bisdodecyl porphyrin, C12P) nanoparticles to fabricate reduced graphene oxide-porphyrin (rGO-P) nanocomposite as well as demonstrates their outstanding removal activity of azo dye and antimicrobial potential. The synthesized porphyrin, rGO, and rGO-P nanocomposites were characterised using SEM, HRTEM, Raman spectroscopy, XRD, 1H-NMR, mass spectrometry, and UV-Visible spectroscopy. The ability of the synthesized rGO-P nanocomposite was then investigated (as catalyst and/or adsorbent) to impact its removal efficacy against Congo red (CR) as a well-known toxic, mutagenic and carcinogenic synthetic dye. The findings indicated that 0.01 g of rGO-P nanocomposite achieved 78.0% removal of CR at pH 3.0. Besides, the removal efficacy was evaluated while studying many aspects i.e. pH, CR initial concentration, and rGO-P nanocomposite amount. Moreover, the minimum inhibitory concentration (MIC) and zone of inhibition (ZOI) of antimicrobial activity against pathogenic bacteria and yeast were evaluated. The antimicrobial results showed that rGO-P nanocomposite revealed the greatest antimicrobial activity against Candida albicans, Enterococcus faecalis, and Staphylococcus aureus with ZOI values of 24.3, 21.8, and 22.1 mm, respectively. Consequently, it demonstrates the substantial potential of rGO-P nanocomposite in the effective removal of pollutant dyes as well as significant antibacterial and antifungal properties.

Pollen-derived microcapsules for aspirin microencapsulation: in vitro release and physico-chemical studies.

Aspirin, also known as acetylsalicylic acid (ASA), is one of the most crucial therapies needed and/or used in a basic health system. Using biocompatible materials to encapsulate ASA would improve its therapeutic efficacy and reduce its side effects via controlled release in physiological environments. Consequently, we explore in this study the feasibility of encapsulation of ASA into robust Lycopodium clavatum L. sporopollenin (LCS) microcapsules. After extracting sporopollenin from their natural micrometer-sized raw spores, the physico-chemical features of the extracted sporopollenin, pure ASA, and sporopollenin loaded with ASA were characterised using various methods, including optical microscopy, Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-vis.) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). Additionally, we demonstrate the in vitro release profile of ASA in a triggered gastrointestinal environment utilizing kinetics analysis to investigate the mechanism of release. The LCS microcapsules were found to be excellent encapsulants for the crucial ASA drug and achieved controlled in vitro release, that would enable further investigations to rationally design versatile controlled delivery platforms.

Encapsulation of folic acid (vitamin B9) into sporopollenin microcapsules: Physico-chemical characterisation, in vitro controlled release and photoprotection study.

Folic acid (FA) is a crucial vitamin for all living creatures. However, it is susceptible to degradation under pH, heat, ultraviolet (UV) and day sunlight conditions, resulting in lowering its bioavailability. Therefore, a versatile protective encapsulation system for FA is highly required to overcome its inherent instability. We report the use of the robust Lycopodium clavatum sporopollenin (LCS) microcapsules, extracted from their natural micrometer-sized raw spores, for FA microencapsulation. The physico-chemical characterisation of the LCS microcapsules are comprehensively investigated before and after the microencapsulation using SEM, elemental, CLSM, FTIR, TGA/DTG and XRD analyses, revealing a successful FA encapsulation within the LCS in an amorphous form. The phenylpropanoid acids, responsible for the UV protection and the autofluorescence of the LCS, were found in the LCS as evidenced by FTIR analysis. TGA/DTG results revealed that the hemi-cellulose and cellulose are the major component of the LCS. A controlled and sustained release of FA from FA-loaded LCS were achieved where the release profile of FA-loaded LCS was found to be pH-dependent. The percentages of cumulative FA released after 10 h at 37 ± 0.5 °C were 45.5% and 76.1% in pH 1.2 and 7.4, respectively, ensuring controlled and slow release in simulated physiological conditions. The FA release kinetic studies indicated the prevalence of the Fickian diffusion mechanism in pH 1.2, while anomalous non-Fickian transport was ascribed for FA release in pH 7.4. The in vitro cytotoxicity assay revealed that the obtained formulations were biocompatible against the human skin fibroblast (HSF) cell line. The versatile LCS microcapsules exhibited intriguing photostability for FA under UV or sunlight irradiation. Concretely, the obtained FA sustained delivery and photoprotection properties of these LCS microcapsules validate their multifunctional characteristics, opening up intriguing applications in oral and topical drug delivery as well as in food industry.

Single-walled carbon nanotube absolute-handedness chirality assignment confirmation using metalized porphyrin's supramolecular structures via STM imaging technique.

This work reports confirmation of the experimental assignment of the absolute-handedness chirality of single-walled carbon nanotubes (SWNTs). This was achieved by applying the scanning tunneling microscopy (STM) imaging technique to a supramolecular composite consisting of a metalized porphyrin derivative (nickel-5,15-bisdodecylporphyrin [Ni-BDP]) affixed to the surfaces of chiral-concentrated SWNTs (with right-handed helix P- and left-handed helix M-). On the basis of the handedness chirality, different chiral supramolecular structures of Ni-BDP were observed on the surfaces of the two SWNT enantiomers. The incorporation of a metal center into the porphyrin ring did not significantly affect the SWNT absolute-handedness chirality assignment, the large pi-system porphyrin ring being the crucial factor. These findings will effectively pave the way towards the clear selective synthesis, separation, chemistry, and applications of SWNT enantiomers.

Assignment of the Absolute-Handedness Chirality of Single-Walled Carbon Nanotubes Using Organic Molecule Supramolecular Structures.

Supramolecular structures of organic molecules on planar nanocarbon surfaces, such as highly oriented pyrolytic graphite (HOPG), have been extensively studied and the factors that control them are generally well-established. In contrast, the properties of supramolecular structures on curved nanocarbon surfaces like carbon nanotubes remain challenging to predict and/or to understand. This paper reports an investigation into the first study of the supramolecular structures of 5,15-bisdodecylporphyrin (C12P) on chiral, concentrated single-walled carbon nanotubes (SWNTs; with right-handed helix P- and left-handed helix M-) surfaces using STM. Furthermore, the study is the first of its kind to experimentally assign the absolute-handedness chirality of SWNTs, as well as to understand their effect on the supramolecular structures of organic molecules on their surfaces. Interestingly, these SWNT enantiomers resulted in supramolecular structures of opposite chirality based on the handedness chirality. With molecular modelling, we predicted the absolute-handedness chirality of SWNTs, before demonstrating this experimentally.

Supramolecular structures of terbium(iii) porphyrin double-decker complexes on a single-walled carbon nanotube surface.

This work mainly reports the observation of novel supramolecular structures of TbIII-5,15-bisdodecylporphyrin (BDP, C12P) double-decker complexes on the surfaces of single-walled carbon nanotubes (SWNTs) performed by scanning tunneling microscopy under an ultra-high vacuum and low temperature, atomic force microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy, and ultraviolet-visible spectroscopy. The molecules formed a well-ordered self-assembled helix-shaped array with regular periodicity on the tube surface. Additionally, some magnetic properties of the BDP-molecule as well as the resulting BDP-SWNT composites were investigated by superconducting quantum interference measurements. The molecule exhibits single-molecule magnetic (SMM) properties and the composite's magnetization increases almost linearly with decreasing temperature which is possibly due to the coupling between porphyrin molecules and SWNTs. Consequently, this may enable the development of more advanced spintronic devices based on porphyrin-nanocarbon composites.