Enhancement of single‑photon emission from nitrogen‑vacancy centers with TiN/(Al,Sc)N hyperbolic metamaterial

The broadband enhancement of single‑photon emission from nitrogen‐vacancy centers in nanodiamonds coupled to a planar multilayer metamaterial with hyperbolic dispersion is studied experimentally. The metamaterial is fabricated as an epitaxial metal/dielectric superlattice consisting of CMOS‐compatible ceramics: titanium nitride (TiN) and aluminum scandium nitride (Al_xSc_1‐xN). It is demonstrated that employing the metamaterial results in significant enhancement of collected single‑photon emission and reduction of the excited‐state lifetime. Our results could have an impact on future CMOS‐compatible integrated quantum sources.

     

Selective,Transition Metal-free 1,2-Diboration of Alkyl Halides,Tosylates, and Alcohols

Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program.     

The Radical Anion,Dianion and Electron Transport Properties of Tetraiodotetraazapentacene

Tetraiodotetraazapentacene I₄TAP , the last missing derivative in the series of halogenated silylated tetraazapentacenes, was synthesized via condensation chemistry from a TIPS-ethynylated diaminobenzothiadiazol in three steps. Single and double reduction furnished its air-stable monoanion and relatively air-stable dianion, both of which were characterized by crystallography. All three species are structurally and spectroscopically compared to non-halogenated TAP and Br₄TAP . I₄TAP is an n-channel material in thin-film transistors with average electron mobilities exceeding 1 cm² (Vs)⁻¹.     

Discovery of Novel Sultone Fused Berberine Derivatives as Promising Tdp1 Inhibitors

A new type of berberine derivatives was obtained by the reaction of berberrubine with aliphatic sulfonyl chlorides. The new polycyclic compounds have a sultone ring condensed to C and D rings of a protoberberine core. The reaction conditions were developed to facilitate the formation of sultones with high yields without by-product formation. Thus, it was shown that the order of addition of reagents affects the composition of the reaction products: when sulfochlorides are added to berberrubine, their corresponding 9-O-sulfonates are predominantly formed; when berberrubine is added to pre-generated sulfenes, sultones are the only products. The reaction was shown to proceed stereo-selectively and the cycle configuration was confirmed by 2D NMR spectroscopy. The inhibitory activity of the synthesized sultones and their 12-brominated analogs against the DNA-repair enzyme tyrosyl-DNA phosphodiesterase 1 (Tdp1), an important target for a potential antitumor therapy, was studied. All derivatives were active in the micromolar and submicromolar range, in contrast to the acyclic analogs and 9-O-sulfonates, which were inactive. The significance of the sultone cycle and bromine substituent in binding with the enzyme was confirmed using molecular modeling. The active inhibitors are mostly non-toxic to the HeLa cancer cell line, and several ligands show synergy with topotecan, a topoisomerase 1 poison in clinical use. Thus, novel berberine derivatives can be considered as candidates for adjuvant therapy against cancer.     

Synthesis and Single Crystal Structures of N-Substituted Benzamides and Their Chemoselective Selenation/Reduction Derivatives

A series of N-aryl-N-(2-oxo-2-arylethyl) benzamides and cinnamides has been prepared. The reaction of the benzamides with Woollins’ reagent, a highly efficient chemoselective selenation/reduction reagent, gave the corresponding N-aryl-N-(arylenethyl) benzoselenoamides in good yields. Five representative single crystal X-ray structures are discussed.     

Quality Evaluation of Light- and Dark-Colored Hungarian Honeys,Focusing on Botanical Origin,Antioxidant Capacity and Mineral Content

Melissopalynology, antioxidant capacity and mineral and toxic element contents were analyzed in eight types of Hungarian honeys. Based on color, two groups were distinguished: light honeys comprised acacia, amorpha, phacelia and linden honeys; while dark honeys included sunflower, chestnut, fennel and sage honeys, with 100 to 300 and 700 to 1500 mAU, respectively. The unifloral origin of each sample was supported using pollen analysis. The absorbance of honey correlated positively with antioxidant capacity determined by three different methods (TRC, DPPH, ORAC), and also with mineral content. The exception was the light amber linden honey with significantly higher K content and antiradical activity than other light honeys. The Mn, Zn and Fe contents were the highest in chestnut, sunflower and fennel honeys, respectively. The black meadow sage honey performed best regarding the content of other elements and antioxidant activity. The concentrations of several toxic elements were below the detection limit in the samples, indicating their good quality. The principal component analysis (PCA) revealed correlations between different antioxidant assays and minerals, and furthermore, confirmed the botanical authentication of the honeys based on the studied parameters. To our best knowledge, the present study is the first to provide a complex analysis of quality parameters of eight unifloral Hungarian honeys.     

Novel Tdp1 Inhibitors Based on Adamantane Connected with Monoterpene Moieties via Heterocyclic Fragments

Tyrosyl-DNA phosphodiesterase 1 (Tdp1) is a promising target for anticancer therapy due to its ability to counter the effects topoisomerase 1 (Top1) poison, such as topotecan, thus, decreasing their efficacy. Compounds containing adamantane and monoterpenoid residues connected via 1,2,4-triazole or 1,3,4-thiadiazole linkers were synthesized and tested against Tdp1. All the derivatives exhibited inhibition at low micromolar or nanomolar concentrations with the most potent inhibitors having IC₅₀ values in the 0.35–0.57 µM range. The cytotoxicity was determined in the HeLa, HCT-116 and SW837 cancer cell lines; moderate CC₅₀ (µM) values were seen from the mid-teens to no effect at 100 µM. Furthermore, citral derivative 20c, α-pinene-derived compounds 20f, 20g and 25c, and the citronellic acid derivative 25b were found to have a sensitizing effect in conjunction with topotecan in the HeLa cervical cancer and colon adenocarcinoma HCT-116 cell lines. The ligands are predicted to bind in the catalytic pocket of Tdp1 and have favorable physicochemical properties for further development as a potential adjunct therapy with Top1 poisons.     

Adaptation of electrodes and printable gel polymer electrolytes for optimized fully organic batteries

Despite intensive scientific efforts on the development of organic batteries, their full potential is still not being realized. The individual components, such as electrode materials and electrolytes, are in most cases developed independently and are not adjusted to each other. In this context, we report on the performance optimization of a full-organic solid-state battery system by the mutual adaptation of the electrode materials and an ionic liquid (IL)-based gel polymer electrolyte (GPE). The formulation of the latter was designed for a one-step manufacturing approach and can be applied directly to the electrode surface, where it is UV-cured to yield the GPE without further post-treatment steps. Herein, a special focus was placed on the applicability in industrial processes. A first significant capacity increase was achieved by the incorporation of the IL into the electrode composite. Furthermore, the GPE composition was adapted applying acrylate- and methacrylate-based monomers and combinations thereof with the premise of a fast curing step. Furthermore, the amount of IL was varied, and all combinations were evaluated for their final performance in cells. The latter variation revealed that a high ionic conductivity is not the only determining factor for a good cell performance. Next to a sufficient conductivity, the interaction between electrode and electrolyte plays a key role for the cell performance as it enhances the accessibility of the counter ions to the redox-active sites.     

Highly Emissive 9-Borafluorene Derivatives: Synthesis,Photophysical Properties and Device Fabrication

A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m⁻². These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.     

2- and 2,7-Substituted para-N-Methylpyridinium Pyrenes: Syntheses,Molecular and Electronic Structures,Photophysical, Electrochemical,and Spectroelectrochemical Properties and Binding to Double-Stranded (ds) DNA

Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm⁻¹. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc⁺ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents.