Additive-Free Chemoselective Acylation of Amines

Aliphatic and aromatic amines are efficiently acylated by acetic, pivalic, benzoic, phthalic, or maleic anhydrides in ethyl acetate at room temperature. Under the same experimental conditions, amino alcohols are chemoselectively acylated at the amino group.     

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.

     

Liquid–Liquid Phase Equilibrium and Ion-Exchange Exploration for Aqueous Two-Phase Systems of ([C4mim]Cl + K2CO3 or K3C6H5O7 + water) at Different Temperatures

Journal of Solution Chemistry - Liquid–liquid equilibrium (LLE) data and phase diagrams for new aqueous two-phase systems (ATPSs) containing 1-butyl-3-methylimidazolium chloride...     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

Conifers Phytochemicals: A Valuable Forest with Therapeutic Potential

Conifers have long been recognized for their therapeutic potential in different disorders. Alkaloids, terpenes and polyphenols are the most abundant naturally occurring phytochemicals in these plants. Here, we provide an overview of the phytochemistry and related commercial products obtained from conifers. The pharmacological actions of different phytochemicals present in conifers against bacterial and fungal infections, cancer, diabetes and cardiovascular diseases are also reviewed. Data obtained from experimental and clinical studies performed to date clearly underline that such compounds exert promising antioxidant effects, being able to inhibit cell damage, cancer growth, inflammation and the onset of neurodegenerative diseases. Therefore, an attempt has been made with the intent to highlight the importance of conifer-derived extracts for pharmacological purposes, with the support of relevant in vitro and in vivo experimental data. In short, this review comprehends the information published to date related to conifers’ phytochemicals and illustrates their potential role as drugs.     

Characterization and compatibility study of desloratadine

Desloratadine (DL) is a selective antagonist of the histamine H₁ receptor, which has been widely used to treat allergic symptoms, and stands out from other drugs in this therapeutic class because it does not cause sedative effects. In the present study, the physico-chemical properties of DL were fully characterized using six analytical techniques such as Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TG/DTG), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, Powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). The DSC curve shows a sharp endothermic event at 158.4 °C, and the TG/DTG curve presents two decomposition events between 178.4 and 451.9 °C. A compatibility study involving DL and nine pharmaceutical excipients generally used in pharmaceutical formulations was performed. Physical binary mixtures of DL with each excipient were prepared in a 1:1 (w/w) ratio. After preparation, the samples were analyzed immediately and the results reveal solid-state interaction with anhydrous lactose, microcrystalline cellulose, magnesium stearate, and stearic acid.     

Semiconductor Quantum Dots as Components of Photoactive Supramolecular Architectures

Luminescent quantum dots (QDs) are colloidal semiconductor nanocrystals consisting of an inorganic core covered by a molecular layer of organic surfactants. Although QDs have been known for more than thirty years, they are still attracting the interest of researchers because of their unique size-tunable optical and electrical properties arising from quantum confinement. Moreover, the controlled decoration of the QD surface with suitable molecular species enables the rational design of inorganic-organic multicomponent architectures that can show a vast array of functionalities. This minireview highlights the recent progress in the use of surface-modified QDs – in particular, those based on cadmium chalcogenides – as supramolecular platforms for light-related applications such as optical sensing, triplet photosensitization, photocatalysis and phototherapy.     

An Efficient RuII–RhIII–RuII Polypyridyl Photocatalyst for Visible‐Light‐Driven Hydrogen Production in Aqueous Solution

The development of multicomponent molecular systems for the photocatalytic reduction of water to hydrogen has experienced considerable growth since the end of the 1970s. Recently, with the aim of improving the efficiency of the catalysis, single‐component photocatalysts have been developed in which the photosensitizer is chemically coupled to the hydrogen‐evolving catalyst in the same molecule through a bridging ligand. Until now, none of these photocatalysts has operated efficiently in pure aqueous solution: a highly desirable medium for energy‐conversion applications. Herein, we introduce a new ruthenium–rhodium polypyridyl complex as the first efficient homogeneous photocatalyst for H₂ production in water with turnover numbers of several hundred. This study also demonstrates unambiguously that the catalytic performance of such systems linked through a nonconjugated bridge is significantly improved as compared to that of a mixture of the separate components.     

Preparation of a new chiral non-racemic sulfur-containing diselenide and applications in asymmetric synthesis

The synthesis of the new chiral non-racemic sulfur-containing diselenide, di-2-methoxy-6-[(1S)-1-(methylthio)ethyl]phenyl diselenide, is described. When treated with ammonium persulfate this diselenide is transformed into the corresponding selenenyl sulfate, which acts as a strong electrophilic reagent and adds to alkenes, in the presence of methanol or water, to afford the products of selenomethoxylation or selenohydroxylation, respectively, with excellent diastereoselectivities. Starting from alkenes containing internal nucleophiles, asymmetric cyclofunctionalization reactions also resulted in good chemical yields, complete regioselectivities, and high diastereoselectivities. This sulfur-containing diselenide can also be used in catalytic amounts to promote one-pot selenenylation-deselenenylation processes, from which several types of products can be obtained in high yield and with good enantiomeric excess.     

Trends in stability of the lanthanide series determined for the TBP—Dilute HNO3 extraction systems

The paper concerns the extraction of lanthanides by TBP from dilute solutions of nitric acid. The results show that the relative free energy associated with the investigated process decreases from La to Sm and the increases up to Lu. The occurrence of a minimum in the free energy changes is explained by the change of coordination number in the first hydration sphere of lanthanide aqua ions between Pm and Gd. The results are discussed in terms of the most probable structures of the extracted species. Outer sphere complexa tion seems to be realized by the Ln³⁺ ions transferring into the organic phase. The estimation of the trends in the enthalpy and entropy terms is under preparation. Up to, 1980 Department of Radiochemistry.