Synthesis of novel 1,2,3-triazolyl nucleoside analogues bearing uracil, 6-methyluracil, 3,6-dimethyluracil,thymine, and quinazoline-2,4-dione moieties

A series of novel 1,2,3-triazolyl nucleoside analogues was synthesized via the CuAAC reaction of N1-alkynyl uracil, 6-methyluracil, 3,6-dimethyl uracil, thymine and quinazolin-2,4-dione with protected azido β-d-ribofuranose. The obtained compounds differ in both the nature of the pyrimidine-2,4-dione fragment and the length of the polymethylene linker connecting it with the β-d-ribofuranosyl-1,2,3-triazol-4-yl moiety. The 1,2,3-triazolyl nucleoside analogues were evaluated for their cytotoxicity in vitro.     

Cyclic Tribismuthide as a Piano Stool Complex Ligand – Synthesis and Crystal Structure of (η3‐Bi3)M(CO)33– (M = Cr,Mo)

The reactions between K₅Bi₄, [(C₆H₆)Cr(CO)₃] or [(C₇H₈)Mo(CO)₃], and [2.2.2]crypt in liquid ammonia yielded the compounds [K([2.2.2]crypt)]₃(η³‐Bi₃)M(CO)₃ · 10NH₃ (M = Cr, Mo), which crystallize isostructurally in P2₁/n. Both contain an 18 valence electron piano‐stool complex with a η³‐coordinated Bi₃‐ring ligand. The Bi–Bi distances range from 2.9560(5) to 2.9867(3) Å and are slightly shorter than known Bi–Bi single bonds but longer than Bi–Bi double bonds. The newly found compounds complete the family of similar complexes with E₃‐ring ligands (E = P‐Bi).     

Dynamic Nuclear Polarization of 13C Nuclei in the Liquid State over a 10 Tesla Field Range

Nuclear magnetic resonance (NMR) techniques play an essential role in natural science and medicine. In spite of the tremendous utility associated with the small energies detected, the most severe limitation is the low signal‐to‐noise ratio. Dynamic nuclear polarization (DNP), a technique based on transfer of polarization from electron to nuclear spins, has emerged as a tool to enhance sensitivity of NMR. However, the approach in liquids still faces several challenges. Herein we report the observation of room‐temperature, liquid DNP ¹³C signal enhancements in organic small molecules as high as 600 at 9.4 Tesla and 800 at 1.2 Tesla. A mechanistic investigation of the ¹³C‐DNP field dependence shows that DNP efficiency is raised by proper choice of the polarizing agent (paramagnetic center) and by halogen atoms as mediators of scalar hyperfine interaction. Observation of sizable DNP of ¹³CH₂ and ¹³CH₃ groups in organic molecules at 9.4 T opens perspective for a broader application of this method.     

Linear‐Dendritic Alternating Copolymers

Herein, the design, synthesis, and characterization of an unprecedented copolymer consisting of alternating linear and dendritic segments is described. First, a 4th‐generation Hawker‐type dendron with two azide groups was synthesized, followed by a step‐growth azide‐alkyne “click” reaction between the 4th‐generation diazido dendron and poly(ethylene glycol) diacetylene to create the target polymers. Unequal reactivity of the functional groups was observed in the step‐growth polymerization. The resulting copolymers, with alternating hydrophilic linear and hydrophobic dendritic segments, can spontaneously associate into a unique type of microphase‐segregated nanorods in water.     

Fluorescent probes on the basis of coumarin derivatives for determining biogenic thiols and thiophenols

Chemistry of Heterocyclic Compounds - In this minireview, we consider the reactivity of fluorescent probes on the basis of coumarin derivatives for the purpose of detecting biogenic thiols...     

Viability of Using Glycerin as a Co-substrate in Anaerobic Digestion of Sugarcane Stillage (Vinasse): Effect of Diversified Operational Strategies

Vinasse, from sugar and ethanol production, stands out as one of the most problematic agroindustry wastes due to its high chemical oxygen demand, large production volume, and recalcitrant compounds. Therefore, the viability of using glycerin as a co-substrate in vinasse anaerobic digestion was tested, to increase process efficiency and biogas productivity. The effect of feeding strategy, influent concentration, cycle length, and temperature were assessed to optimize methane production. Glycerin (1.53% v/v) proved to be a good co-substrate since it increased the overall methane production in co-digestion assays. CH₄ productivity enhanced exponentially as influent concentration increased, but when temperature was increased to 35 °C, biogas production was impaired. The highest methane productivity and yield were achieved using fed-batch mode, at 30 °C and at an organic loading rate of 10.1 kg COD m⁻³ day⁻¹: 139.32 mol CH₄ m⁻³ day⁻¹, 13.86 mol CH₄ kg COD_applied, and 15.30 mol CH₄ kg COD_removed. Methane was predominantly produced through the hydrogenotrophic route. In order to treat all the vinasse produced by a mid-size sugar and ethanol plant, nine reactors with 7263.4 m³ each would be needed. The energy generated by burning the biogas in boilers would reach approximately 92,000 MW h per season and could save up to US$ 240,000.00 per month in diesel oil demand.

     

Interference of Metal Oxide Nanoparticles with Coagulation Cascade and Interaction with Blood Components

Metal oxide nanoparticles (NPs) are increasingly used for different purposes, showing a potential risk on human health. The analysis of the interaction of these metal oxide NPs with blood components is a crucial step in the characterization of their biocompatibility, but information available of comparative studies with several doses and different metal oxide NPs is really scarce. In this study, six different metal oxide NPs (TiO₂, CeO₂, Al₂O₃, Y₂O₃, and two different types of ZnO NPs) at different concentrations are used, and their potential adverse effects on blood are determined. Both, prothrombin time (PT) and activated partial thromboplastin time (aPTT), are assessed to understand particle influence on the plasma coagulation cascade. Additional hematocompatibility tests include assessment of thrombin coagulation time, platelet aggregation, leukocyte procoagulant activity (PCA), hemolysis, and complement activation. The results demonstrate that only the ZnO and TiO₂ NPs affect the coagulation cascade by increasing the aPTT in a dose‐dependent manner. Moreover, ZnO NPs increase PT, while TiO₂ NPs induce a decrease in the PT. In addition to affecting coagulation time, ZnO NPs also induce platelet aggregation and leukocyte PCA. All tested metal oxide NPs do not affect hemolysis and complement activation.     

PLA Electrospun Fibers Reinforced with Organic and Inorganic Nanoparticles: A Comparative Study

In this work, different poly (lactic acid) (PLA)-based nanocomposite electrospun fibers, reinforced with both organic and inorganic nanoparticles, were obtained. As organic fibers, cellulose nanocrystals, CNC, both neat and functionalized by “grafting from” reaction, chitosan and graphene were used; meanwhile, hydroxyapatite and silver nanoparticles were used as inorganic fibers. All of the nanoparticles were added at 1 wt% with respect to the PLA matrix in order to be able to compare their effect. The main aim of this work was to study the morphological, thermal and mechanical properties of the different systems, looking for differences between the effects of the addition of organic or inorganic nanoparticles. No differences were found in either the glass transition temperature or the melting temperature between the different electrospun systems. However, systems reinforced with both neat and functionalized CNC exhibited an enhanced degree of crystallinity of the electrospun fibers, by up to 12.3%. From a mechanical point of view, both organic and inorganic nanoparticles exhibited a decreased elastic modulus and tensile strength in comparison to neat electrospun PLA fibers, improving their elongation at break. Furthermore, all of the organic and inorganic reinforced systems disintegrated under composting conditions after 35 days.     

Integratomics of Human Dermal Fibroblasts Treated with Low Molecular Weight Hyaluronic Acid

Hyaluronic acid (HA) is a glycosaminoglycan very common in commercial products from pharmaceuticals to cosmetics due to its widespread distribution in humans and its diversified physico-chemical proprieties. Despite its extended use and preliminary evidence showing even also opposite activities to the native form, the precise cellular effects of HA at low-molecular-weight (LWM-HA) are currently unclear. The ‘omics sciences currently in development offer a new and combined perspective on the cellular and organismal environment. This work aims to integrate lipidomics analyses to our previous quantitative proteomics one for a multi-omics vision of intra- and extra-cellular impact of different concentrations (0.125, 0.25, and 0.50%) of LMW-HA (20–50 kDa) on normal human dermal fibroblasts by LC-high resolution mass spectrometry (LC-HRMS). Untargeted lipidomics allowed us to identify 903 unique lipids mostly represented by triacylglycerols, ceramides, and phosphatidylcholines. According to proteomics analyses, LMW-HA 0.50% was the most effective concentration also in the lipidome rearrangement especially stimulating the synthesis of ceramides involved in skin hydration and reparation, cell signaling, and energy balance. Finally, integrative analyses showed 25 nodes covering several intra- and extra-cellular functions. The more complete comprehension of intra- and extra-cellular effects of LMW-HA here pointed out will be useful to further exploit its features and improve current formulations even though further studies on lipids biosynthesis and degradation are necessary.