"Nanoantibiotics": a new paradigm for treating infectious diseases using nanomaterials in the antibiotics resistant era.

and Applications of Fullerenes, Carbon Dots, Nanotubes, Graphene, Nanodiamonds, and Combined Superstructures Vasilios Georgakilas,† Jason A. Perman,‡ Jiri Tucek,‡ and Radek Zboril*,‡ †Material Science Department, University of Patras, 26504 Rio Patras, Greece ‡Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University in Olomouc, 17 listopadu 1192/12, 771 46 Olomouc, Czech Republic

Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures.

The review covers the knowledge on photoremovable protecting
groups and includes all relevant chromophores studied in the
time period of 2000–2012; the most relevant earlier works are
also discussed.

/pdf/photoremovable-protecting-groups-in-chemistry-and-biology-2n33qs6p7b.pdf

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Crown ethers: sensors for ions and molecular scaffolds for materials and biological models.

Carbon Nanomaterials for Biological Imaging and Nanomedicinal Therapy

Using a novel hydrogen peroxide heating method, we synthesized milky white, water-soluble polyhydroxylated fullerenes (fullerenols) with 36-40 hydroxyl groups (estimated average) along with 8-9 secondary bound water molecules. The fullerenols exhibited high water solubility up to 58.9 mg/mL in a neutral (pH = 7) condition. Dynamic light scattering analysis showed a high dispersion property, to give a narrow particle size distribution within 0.7-2.0 nm.

Facile synthesis of highly water-soluble fullerenes more than half-covered by hydroxyl groups.

A water-soluble polyhydroxylated fullerene, i.e. a fullerenol, with 44 hydroxyl groups and 8 secondary bound water molecules, C60(OH)44·8H2O (estimated average structure), has been synthesized in a facile one step reaction from pristine C60 by hydroxylation with hydrogen peroxide in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydroxide (TBAH), under organic/aqueous bilayer conditions. The fullerenol exhibited high water solubility, up to 64.9 mg/mL, under neutral (pH = 7) conditions. Dynamic light-scattering (DLS) analysis showed a narrow particle size distribution, of 1–2 nm, indicating that the fullerenol had high dispersion properties in water. The results of particle size analyses, which both focused on a single nanoregion and were conducted using a novel induced grating (IG) method and a scanning probe microscope (SPM), were consistent with the DLS results. A plausible reaction mechanism, which includes fullerene oxide intermediates detected by liquid chromatography-mass spectrometry (LC-MS), has been proposed.

Facile and Scalable Synthesis of a Highly Hydroxylated Water-Soluble Fullerenol as a Single Nanoparticle

The antimicrobial activities of fullerene C60 and its derivatives against 6 kinds of bacteria and 2 kinds of fungi were evaluated. The tested samples were water-soluble fullerenes (polyvinylpyrrolidone (PVP)/C60, γ-cyclodextrin (γ-CD)/C60, and nano-C60) and 3 types of fullerenols (C60(OH)12, C60(OH)36·8H2O, and C60(OH)44·8H2O). Their activities were compared with those of (+)-catechin and hinokitiol from the viewpoint of future application to cosmetics. Although pristine C60 demonstrated no antimicrobial activity, fullerenols exhibited good antimicrobial activity against Propionibacterium acnes, Staphylococcus epidermidis, Candida albicans, and Malassezia furfur. In particular, C60(OH)44 exhibited a strong and wide-ranging antimicrobial activity comparable to that of catechin. This compound exhibits antimicrobial activity via inhibition of microbial cell growth and not via bactericidal activity.

Antimicrobial activity of fullerenes and their hydroxylated derivatives.

We studied the kinetics of the Diels-Alder reaction of Li(+)-encapsulated [60]fullerene with 1,3-cyclohexadiene and characterized the obtained product, [Li(+)@C60(C6H8)](PF6(-)). Compared with empty C60, Li(+)@C60 reacted 2400-fold faster at 303 K, a rate enhancement that corresponds to lowering the activation energy by 24.2 kJ mol(-1). The enhanced Diels-Alder reaction rate was well explained by DFT calculation at the M06-2X/6-31G(d) level of theory considering the reactant complex with dispersion corrections. The calculated activation energies for empty C60 and Li(+)@C60 (65.2 and 43.6 kJ mol(-1), respectively) agreed fairly well with the experimentally obtained values (67.4 and 44.0 kJ mol(-1), respectively). According to the calculation, the lowering of the transition state energy by Li(+) encapsulation was associated with stabilization of the reactant complex (by 14.1 kJ mol(-1)) and the [4 + 2] product (by 5.9 kJ mol(-1)) through favorable frontier molecular orbital interactions. The encapsulated Li(+) ion catalyzed the Diels-Alder reaction by lowering the LUMO of Li(+)@C60. This is the first detailed report on the kinetics of a Diels-Alder reaction catalyzed by an encapsulated Lewis acid catalyst rather than one coordinated to a heteroatom in the dienophile.

Kinetic study of the Diels-Alder reaction of Li⁺@C₆₀ with cyclohexadiene: greatly increased reaction rate by encapsulated Li⁺.

We investigated the antioxidant activity of supramolecular water-soluble fullerenes, polyvinylpyrrolidone (PVP)-entrapped C(60), and gamma-cyclodextrin (CD)-bi-capped C(60), based on comparable beta-carotene bleaching assay. Antioxidant activity against reactive oxygen species (ROS) generated by three different methods, (i) autoxidation of linoleic acid, (ii) hydrogen peroxide promoter, and (iii) photoirradiation, was evaluated as percent of inhibition relative to a control experiment in view of the bleaching rate constant (k(obs)) as well as the persistent absorbency of beta-carotene. Water-soluble fullerenes exhibit significant inhibitory effects on the oxidative discoloration of beta-carotene in any system.

https://www.tandfonline.com/doi/pdf/10.1271/bbb.60491

Takumi Oshima

Papers

Facile synthesis of highly water-soluble fullerenes more than half-covered by hydroxyl groups.

Facile and Scalable Synthesis of a Highly Hydroxylated Water-Soluble Fullerenol as a Single Nanoparticle

Antimicrobial activity of fullerenes and their hydroxylated derivatives.

Kinetic study of the Diels-Alder reaction of Li⁺@C₆₀ with cyclohexadiene: greatly increased reaction rate by encapsulated Li⁺.

Antioxidant Activity of Supramolecular Water-Soluble Fullerenes Evaluated by β-Carotene Bleaching Assay