First Synthesis of the Inherently Chiral Trans-4′ Bisadduct of C59N Azafullerene by Using Cyclo-[2]-dodecylmalonate as a Tether

The multiaddition chemistry of azafullerene C₅₉N has been scarcely explored, and the isolation of pure bisadducts is in its infancy. Encouraged by the recent regioselective synthesis of the inherently chiral equatorial_face bisadduct of C₅₉N, we focused on the isolation of the first trans-4 bisadduct in a simple two-step approach. The first regioselective synthesis of the trans-4 bisadduct of C₅₉N by using cyclo-[2]-dodecylmalonate as a tether is now reported. The newly synthesized bisadduct has C₁ symmetry, as evidenced by ¹³C NMR, while X-ray crystallography validated the trans-4′ addition pattern. Furthermore, the inherently chiral trans-4′ C₅₉N bisadduct was enantiomerically resolved, and the mirror-image relation of the two enantiomers was probed by circular dichroism spectroscopy. Finally, UV-Vis and redox assays suggested that the addition pattern has a reflection in the light-harvesting and redox properties of the bisadduct.     

On the correlation of the Thue–Morse sequence

The Ramanujan Journal - Let $$s_{q}$$ denote the sum of digits function in base q. The aim of this work is to estimate the exponential sums involving the sum of digits of shifted integers, namely...     

Synthesis of PAN/ferrocyanide composite incorporated with cetrimonium bromide and its employment as a bifunctional adsorbent for coremoval of Cs+ and HCrO4− from aqueous solutions

Polyacrylonitrile/ferrocyanide composite incorporated with cetrimonium bromide (PFICB) was synthesized and evaluated as a novel bifunctional adsorbent for coremoval of Cs⁺ and HCrO₄^?. Results of the reaction time effect showed that adsorption of Cs⁺ and HCrO₄^? onto PFICB were rapid processes. The effect of the solution pH in the range 2.5–10 revealed that PFICB had the ability to simultaneously remove Cs⁺ and HCrO₄^?. The maximum adsorption capacity of PFICB was found to be 41.79 mg/g for Cs⁺ and 19.39 mg/g for HCrO₄^?. These values were compared with those reported in literature using other adsorbents.

     

Superacid-Mediated Late-Stage Aromatic Polydeuteration of Pharmaceuticals

The field of medicinal chemistry is currently witnessing a deuterium rush owing to the remarkable properties of this element as bioisoster of hydrogen atom. Aromatic hydrogen isotope exchange (HIE) is one of the most studied strategies nowadays as it promises to access deuterium-modified drugs directly from their non-labeled parents. While most of the recent studies focus on metal-catalyzed C−H activation strategy, the use of superacidic conditions has been largely overlooked. This study shows that the use of TfOD as reaction medium allows the late-stage polydeuteration of a broad library of pharmaceuticals bearing a wide array of functional groups, complementing existing procedures.     

Highly Enantioselective Hydrogenation of β‐Alkyl and β‐(ω‐Chloroalkyl) Substituted β‐Keto Esters

Highly enantioselective hydrogenation of β‐alkyl and β‐(ω‐chloroalkyl) substituted β‐keto esters was achieved with Ru catalysts based on chiral diphosphines in EtOH at 50°C under 50‐bar initial hydrogen pressure, affording the corresponding β‐hydroxy esters in >98% ee.     

A Light‐up Logic Platform for Selective Recognition of Parallel G‐Quadruplex Structures via Disaggregation‐Induced Emission

The design of turn‐on dyes with optical signals sensitive to the formation of supramolecular structures provides fascinating and underexplored opportunities for G‐quadruplex (G4) DNA detection and characterization. Here, we show a new switching mechanism that relies on the recognition‐driven disaggregation (on‐signal) of an ultrabright coumarin‐quinazoline conjugate. The synthesized probe selectively lights‐up parallel G4 DNA structures via the disassembly of its supramolecular state, demonstrating outputs that are easily integrable into a label‐free molecular logic system. Finally, our molecule preferentially stains the G4‐rich nucleoli of cancer cells.     

Simultaneous quantification of total eicosapentaenoic acid,docosahexaenoic acid and arachidonic acid in plasma by high‐performance liquid chromatography–tandem mass spectrometry

A method for the simultaneous quantification of eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and arachidonic acid (AA) in human plasma by HPLC–tandem mass spectrometry (HPLC‐MS/MS) was developed and validated. Free and esterified forms of fatty acids were hydrolysed from plasma samples in the presence of an internal standard and subjected to liquid–liquid extraction. The chromatographic run time was 3.5 min per sample. The assay was linear from 0.5 to 300 mg/L (r² > 0.997, n = 18). Based on matrix addition, accuracy deviation was <15%, except for AA at 10 mg/L (30–90%), whereas precision was <8% for all fatty acids studied. The method was applied to the measurement of these omega‐3 fatty acids in a fish oil supplement study with healthy volunteers. Healthy males (n = 4) were administered a supplement containing 465 mg EPA and 375 mg DHA per capsule (Omacor®). A dose of two capsules was given daily over a 4 week period. Pre‐treatment concentrations varied between subjects for EPA (17–68 mg/L), DHA (36–63 mg/L) and AA (121–248 mg/L). During the dosing period EPA increased 460–480% from the baseline concentration, while DHA increased 150–160%. The EPA–AA ratio increased from 0.07–0.56 to 0.3–3.1 after 4 weeks of dosing. In conclusion, the method described could be suitable for monitoring EPA, DHA and AA in clinical studies that may aid in achieving optimal concentrations of these fatty acids in patients who could be at risk of sudden cardiac death. Copyright © 2010 John Wiley & Sons, Ltd.     

Pristine and supported ZnO-based catalysts for phenazopyridine degradation with direct solar light

In search for safe techniques to manage waste pharmaceutical compounds drained in water, solar-driven degradation of phenazopyridine (a model drug) was investigated in aqueous media using different ZnO-based catalyst systems. Naked ZnO, CdS-sensitized ZnO (ZnO/CdS) and activated carbon-supported ZnO (AC/ZnO) have been studied. Both naked ZnO and AC/ZnO were highly efficient in mineralizing phenazopyridine, reaching complete removal in ～50 min, with AC/ZnO having the higher edge. The ZnO/CdS system showed lower efficiency, due to screening of light by CdS. Moreover, the tendency of CdS to leach out Cd²⁺ ions discouraged the use of CdS as sensitizer in this work. In both ZnO and AC/ZnO systems, the photo-degradation reaction was induced by the UV tail of the solar light. The visible region, with wavelength longer than 400 nm, failed to induce photo-degradation. The reaction was faster with higher catalyst loading, until a maximum efficiency was reached at a certain concentration. The rate of reaction increased with higher drug concentrations up to a certain limit. The effect of pH value was studied, and the catalysts showed highest efficiencies at pH close to 7. Stability of ZnO to degradation was studied. Both catalyst systems showed lowered efficiencies on recovery and reuse. The results suggest that complete mineralization of waste drugs, commonly dumped in sewage water, with direct solar light is a potentially feasible strategy using the AC/ZnO catalyst.