Synthesis of azahelicenes through Mallory reaction of imine precursors: corannulene substrates provide an exception to the rule in oxidative photocyclizations of diarylethenes.

Typically, the synthesis of phenanthrene-based polycyclic aromatic hydrocarbons relies on the Mallory reaction. In this approach, stilbene (PhCH[double bond, length as m-dash]CHPh)-based precursors undergo an oxidative photocyclization reaction to join the two adjacent aromatic rings into an extended aromatic structure. However, if one C[double bond, length as m-dash]C carbon atom is replaced by a nitrogen atom (C[double bond, length as m-dash]N), the synthesis becomes practically infeasible. Here, we show the very first examples of a successful Mallory reaction on stilbene-like imine precursors involving the molecularly curved corannulene nucleus. The isolated yields exceed 90% and the resulting single and double aza[4]helicenes exhibit adjustable high affinity for electrons.

Corannulene-Based Electron Acceptors: Combining Modular and Practical Synthesis with Electron Affinity and Solubility.

It is shown in this work that high electron affinity can be combined with high solubility and practical accessibility in corannulene-based electron acceptors. The electron affinity originates from the presence of three different types of electron-withdrawing groups (imide, sulfone, and trifluoromethyl) on the aromatic scaffold. The imide substituent further hosts a long alkyl chain (C18 H37 ) to boast solubility in a wide range of organic solvents. The synthesis is modular and consists of three simple steps from a commonly available corannulene derivative with an overall isolated yield of 22-27 %.

Cloisite Microrobots as Self-Propelling Cleaners for Fast and Efficient Removal of Improvised Organophosphate Nerve Agents.

Naturally available microclays are well-known materials with great adsorption capabilities that are available in nature in megatons quantities. On the contrary, artificial nanostructures are often available at high cost via precision manufacturing. Such precision nanomanufacturing is also typically used for fabrication of self-propelled micromotors and nanomachines. Herein, we utilized naturally available Cloisite microclays to fabricate autonomous self-propelled microrobots and demonstrated their excellent performances in pesticide removal due to their excellent adsorption capability. Six different modified Cloisite microrobots were investigated by sputtering their microclays with platinum (Pt) for the fabrication of platinum-Cloisite (Pt-C) microrobots. The obtained microrobots displayed fast velocities (v > 110 µm/s) with fast and efficient enhanced removal of the pesticide fenitrothion, which is also considered as improvised nerve agent. The fabricated Pt-C microrobots exhibited low cytotoxicity even at high concentrations when incubated with human lung carcinoma epithelial cells, which make them safe for human handling.

Substantially higher concentrations of mercury are detected in airborne particulate matter when using a preservation agent during sample preparation steps.

Inductively coupled plasma - mass spectrometry (ICP-MS) analysis of airborne particulate bound mercury was carried out utilizing a high sulfur containing organic compound as a preservation agent to limit the negative bias that affects the determination of low levels of mercury. Between 600% and 1000% more Hg was detected with the use of the additive, lithium tetrathiafulvalene carboxylate (LiCTTF), during the microwave assisted acid digestion sample processing step without influencing the determination of other trace elements. The average Hg concentration was 0.05 ng m-3 and 0.4 ng m-3 in the absence and presence of LiCTTF, respectively. Stabilization of the mercury ions with the preservation agent resulted in higher precision for ICP-MS measurements with relative standard deviation (RSD) values ranging from 1.07% to 4.36%. The results obtained in this study emphasize the necessity of using a preservation agent in the atomic spectroscopic determination of mercury to prevent losses and is especially critical in low-level analyses such as those routinely performed in environmental mercury pollution trend assessments.

A general approach to non-fullerene electron acceptors based on the corannulene motif.

Here, we show that oxidation of exo-cyclic sulfur atoms enhances the molecular reduction potential of non-planar polycyclic aromatic hydrocarbons and allows for a systematic bridging of the electron affinity gap between corannulene, a fragment of fullerene C60, and the prevalent fullerene-based electron acceptor phenyl-C61-butyric acid methyl ester (PCBM).

Photochemical Synthesis and Electronic Properties of Extended Corannulenes with Variable Fluorination Pattern.

The first family of extended and fluorinated corannulenes is prepared through a highly efficient and modular synthetic strategy. In this strategy, corannulene aldehyde could be combined with the fluorine-carrying phosphonium ylides to furnish stilbene-like vinylene precursors. A photochemically induced oxidative cyclization process of these precursors gives rise to the fluorinated and curved polycyclic aromatic hydrocarbons. A UV-vis absorption study shows that aromatic extension results in a bathochromic shift of about 12 nm. Fluorination further shifts the absorption spectrum to the red region, and a maximum shift of about 22 nm is detected for a compound carrying two trifluoromethyl groups. A cyclic and square-wave voltammetry investigation reveals that the extension of the corannulene scaffold increases the reduction potential by 0.11 V. Placement of fluorine or trifluoromethyl groups further enhances the electron affinities. In this regard, the presence of one trifluoromethyl group equals the effect of three aromatic fluorine atoms. Molecules with two trifluoromethyl groups, meanwhile, exhibit the highest reduction potentials of -1.93 and -1.83 V. These values are 0.37 and 0.46 V higher than those of the parental corannulene and demonstrate the utility of the present design concept by efficiently accessing effective electron acceptors based on the buckybowl motif.

Tetrathiafulvalene aids in the atomic spectroscopic determination of total mercury.

The determination of mercury simultaneously with other elements via inductively coupled plasma-mass spectrometry (ICP-MS) in airborne particulate matter (PM2.5) is still challenging due to the lack of accuracy for the low level mercury concentrations as a result of its volatility and tendency to adhere to the walls of the sample introduction system. This study investigated the effect of existing (gold and methionine) and new (lithium tetrathiafulvalene carboxylate (LiCTTF)) preservation agents in order to improve the determination of trace mercury in PM2.5 samples. Statistical analysis revealed that a concentration of 10 µg mL-1 of LiCTTF was sufficient to obtain highly accurate results with t values of 0.1044-1.1239 which are considerably less than the critical t value of 1.8 and apparent recoveries of 85-100%. An evaluation of the method revealed a spiked mercury recovery of 91% and a detection limit of 0.05 ng mL-1. The method was tested for the determination of trace metals in PM2.5 from atmospheric samples and led to the detection of low elemental concentrations in Singapore's atmosphere. The mechanism for the interaction of mercury with LiCTTF and tetrathiafulvalene (TTF) was studied by conducting in situ electrochemical studies. Cyclic voltammetry and square-wave voltammetry analyses of mercury, and mercury in presence of LiCTTF and TTF revealed complexation between the metal and sulfur-containing compounds.

Near infrared light-mediated photoactivation of cytotoxic Re(i) complexes by using lanthanide-doped upconversion nanoparticles.

Platinum-based chemotherapy, although it has been well proven to be effective in the battle against cancer, suffers from limited specificity, severe side effects and drug resistance. The development of new alternatives with potent anticancer effects and improved specificity is therefore urgently needed. Recently, there are some new chemotherapy reagents based on photoactive Re(i) complexes which have been reported as promising alternatives to improve specificity mainly attributed to the spatial and temporal activation process by light irradiation. However, most of them respond to short-wavelength light (e.g. UV, blue or green light), which may cause unwanted photo damage to cells. Herein, we demonstrate a system for near-infrared (NIR) light controlled activation of Re(i) complex cytotoxicity by integration of photoactivatable Re(i) complexes and lanthanide-doped upconversion nanoparticles (UCNPs). Upon NIR irradiation at 980 nm, the Re(i) complex can be locally activated by upconverted UV light emitted from UCNPs and subsequently leads to enhanced cell lethality. Cytotoxicity studies showed effective inactivation of both drug susceptible human ovarian carcinoma A2780 cells and cisplatin resistant subline A2780cis cells by our UCNP based system with NIR irradiation, and there was minimum light toxicity observed in the whole process, suggesting that such a system could provide a promising strategy to control localized activation of Re(i) complexes and therefore minimize potential side effects.