Co(Salox)-Catalyzed Enantioselective Reduction of α,β-Unsaturated Esters

Co-Salox complexes are suitable catalysts for the reduction of prochiral α,β-unsaturated esters. These ligands can be prepared in a single step from available and inexpensive materials, thus representing an easily accessible alternative to previously reported Co-catalysts. NaBH₄ is employed as reducing agent in the presence of EtOH as proton source, leading to the stereoselective formation of chiral esters, amides, and nitriles in up to 99 % yield and 96.5 : 3.5 er. The concentration of the reductant counter cation (Na⁺) and the solvent polarity have been shown to correlate with reactivity and enantioselectivity, suggesting that a relatively complex mechanistic manifold is in place.     

C−H Fluoromethoxylation of Arenes by Photoredox Catalysis

Redox-active N-(fluoromethoxy)benzotriazoles were made accessible from fluoroacetic acid and hydroxybenzotriazoles via electrodecarboxylative coupling. After alkylation, they become effective monofluoromethoxylation reagents, enabling the photocatalytic C−H functionalization of arenes. Thus, irradiation of 1-(OCH₂F)-3-Me-6-(CF₃)benzotriazolium triflate with blue LED light in the presence of [Ru(bpy)₃(PF₆)₂] promotes the synthesis of diversely functionalized aryl monofluoromethyl ethers. This method allows the late-stage functionalization of biologically relevant structures without relying on ecologically problematic halofluorocarbons.     

Site-Specific Ubiquitination of Tau Amyloids Promoted by the E3 Ligase CHIP

Post-translational modifications of Tau are emerging as key players in determining the onset and progression of different tauopathies such as Alzheimer's disease, and are recognized to mediate the structural diversity of the disease-specific Tau amyloids. Here we show that the E3 ligase CHIP catalyzes the site-specific ubiquitination of Tau filaments both in vitro and in cellular models, proving that also Tau amyloid aggregates are direct substrate of PTMs. Transmission electron microscopy and mass spectrometry analysis on ubiquitin-modified Tau amyloids revealed that the conformation of the filaments restricts CHIP-mediated ubiquitination to specific positions of the repeat domain, while only minor alterations in the structure of the fibril core were inferred using seeding experiments in vitro and in a cell-based tauopathy model. Overexpression of CHIP significantly increased the ubiquitination of exogenous PHF, proving that the ligase can interact and modify Tau aggregates also in a complex cellular environment.     

Point-of-Care Testing for the Detection of MicroRNAs: Towards Liquid Biopsy on a Chip

Point-of-care (PoC) testing is revolutionizing the healthcare sector improving patient care in daily hospital practice and allowing reaching even remote geographical areas. In the frame of cancer management, the design and validation of PoC enabling the non-invasive, rapid detection of cancer markers is urgently required to implement liquid biopsy in clinical practice. Therefore, focusing on stable blood-based markers with high-specificity, such as microRNAs, is of crucial importance. In this work, we highlight the potential impact of circulating microRNAs detection on cancer management and the crucial role of PoC testing devices, especially for low-income countries. A detailed discussion about the challenges that should be faced to promote the technological transfer and clinical use of these tools has been added, to provide the readers with a complete overview of potentialities and current limitations.     

Photobleaching Kinetics and Effect of Solvent in the Photophysical Properties of Indocyanine Green for Photodynamic Therapy

Indocyanine green is an attractive molecule for photodynamic therapy due to its near infrared absorption, resulting in a higher tissue penetration. However, its quantum yields of the triplet and singlet state have been reported to be low and then, reactive oxygen species are unlikely to be formed. Aiming to understand the ICG role in photodynamic response, its photobleaching behavior in solution has been studied under distinct conditions of CW laser irradiation at 780 and 808 nm, oxygen saturations and solvents. Sensitizer bleaching and photoproduct formation were measured by absorption spectroscopy and analyzed using the PDT bleaching macroscopic model to extract physical parameters. ICG photobleaching occurs even at lower oxygen concentrations, indicating that the molecule presents more than one way of degradation. Photoproducts were produced even in solution of less than 4 % oxygen saturation for both solvents and excitation wavelengths. Also, the amplitude of absorption related to J-dimers was increased during irradiation, but only in 50 % PBS solution. The formation of photoproducts was enhanced in the presence of J-type dimers under low oxygen concentration, and the quantum yields of triplet and singlet states were one order of magnitude and two times higher, respectively, when compared to ICG in distilled H₂O.     

Infrared Diffusion-Ordered Spectroscopy Reveals Molecular Size and Structure**

Inspired by ideas from NMR, we have developed Infrared Diffusion-Ordered Spectroscopy (IR-DOSY), which simultaneously characterizes molecular structure and size. We rely on the fact that the diffusion coefficient of a molecule is determined by its size through the Stokes–Einstein relation, and achieve sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration in an IR-frequency resolved manner. Analogous to NMR-DOSY, a two-dimensional IR-DOSY spectrum has IR frequency along one axis and diffusion coefficient (or equivalently, size) along the other, so the chemical structure and the size of a compound are characterized simultaneously. In an IR-DOSY spectrum of a mixture, molecules with different sizes are nicely separated into distinct sets of IR peaks. Extending this idea to higher dimensions, we also perform 3D-IR-DOSY, in which we combine the conformation sensitivity of femtosecond multi-dimensional IR spectroscopy with size sensitivity.     

Odd-dimensional counterparts of abelian complex and hypercomplex structures

We introduce the notion of abelian almost contact structures on an odd-dimensional real Lie algebra $\mathfrak{g}$. We investigate correspondences with even-dimensional Lie algebras endowed with an abelian complex structure, and with Kähler Lie algebras when $\mathfrak{g}$ carries a compatible inner product. The classification of 5-dimensional Sasakian Lie algebras with abelian structure is obtained. Later, we introduce abelian almost 3-contact structures on real Lie algebras of dimension $4n+3$, obtaining the classification of these Lie algebras in dimension 7. Finally, we deal with the geometry of a Lie group G endowed with a left invariant abelian almost 3-contact metric structure. We determine conditions for G to admit a canonical metric connection with skew torsion, which plays the role of the Bismut connection for hyperKähler with torsion (HKT) structures arising from abelian hypercomplex structures. We provide examples and discuss the parallelism of the torsion of the canonical connection.