Titanium-Oxo Clusters, Versatile Nanobuilding Blocks for the Design of Advanced Hybrid Materials

Summary. This review describes the major advances made on titanium-oxo clusters chemistry and their derived hybrid materials. The main synthesis procedures, the cluster structures presented in literature, and the relation between the titanium-oxo clusters condensation degree and poisoning ratio are discussed. The tuned organo-functionalisation of the titanium-oxo based nanobuilding blocks allows to develop a LEGO-like chemistry, able to direct the assembling of a large variety of structurally well defined complex hybrid architectures.     

Theory of alkyl-terminated silicon quantum dots

We have carried out a series of ab initio calculations to investigate changes in the optical properties of Si quantum dots as a function of surface passivation. In particular, we have compared hydrogen-passivated dots with those having alkyl groups at the surface. We find that, while on clusters with reconstructed surfaces complete alkyl passivation is possible, steric repulsion prevents full passivation of Si dots with unreconstructed surfaces. In addition, our calculations show that steric repulsion may have a dominant effect in determining the surface structure and eventually the stability of alkyl-passivated clusters, with results dependent on the length of the carbon chain. Alkyl passivation weakly affects optical gaps of silicon quantum dots, while it substantially decreases ionization potentials and electron affinities and affects their excited state properties. On the basis of our results, we propose that alkyl-terminated quantum dots may be size selected, taking advantage of the change in ionization potential as a function of the cluster size.     

Size and structure dependence of carbon monoxide chemisorption on cobalt clusters

We have carried out a series of ab initio calculations to investigate changes in the structural and magnetic properties of pristine cobalt clusters upon CO chemisorption. Our results show that binding energies of CO to 13-55 atom (0.5-1.5 nm) cobalt nanoparticles and preferred chemisorption sites depend on the cluster structure (whether fcc or icosahedral), size, and surface coverage. In addition, we find a strong influence of CO on the magnetism of the cluster, leading to magnetic moments smaller than in the bulk, at variance with pristine clusters which have magnetic moments larger than the bulk. Our findings suggest important changes in catalytic properties of cobalt at the nanoscale. Our theory suggests that at the nanoscale cluster size and surface coverage might control catalysis.     

Reaction of sulfene with heterocyclic N,N-disubstituted α-aminomethyleneketones. VIII. Synthesis of furo[2,3-h]-1,2-benzoxathiin derivatives

Cycloaddition of sulfene to N,N-disubstituted (E)5-aminomethylene-6,7-dihydrobenzo[b]furan-4(5H)ones I gave, only in the case of aliphatic N-substitution and generally in satisfactory yields, N,N-disubstituted 4-amino-3,4,5,6-tetrahydrofuro[2,3-h]-1,2-benzoxathiin 2,2-dioxides II, which are derivatives of the new heterocyclic system furo[2,3-h]-1,2-benzoxathiin. The 4-dimethylamino and 4-piperidino cycloadducts IIa,e were dehydrogenated with DDQ to the corresponding 4-dialkylamino-3,4-dihydrofuro[2,3-h]-1,2-benzoxathiin 2,2-dioxides IIIa,e in low yield. Compounds IIIa,e were tested for photobiological activity and found to be inactive.     

Reaction of ketenes with N,N-disubstituted α-aminomethyleneketones. XVII. Synthesis of 2H-[1]benzothiepino[5,4-b]pyran derivatives

1,4-Cycloaddition of dichloroketene to a number of N,N-disubstituted (E)-4-amino methylene-3,4-dihydro-[1]benzothiepin-5(2H)-ones gave in excellent yield N,N-disubstituted 4-amino-3,3-dichloro-3,4,5,6-tetrahydro-2H-[1]benzothiepino[5,4-b]pyran-2-ones III, which are derivatives of the 2H-[1]benzothiepino[5,4-b]pyran system. Dehydrochlorination of III with DBN afforded N,N-disubstituted 4-amino-3-chloro-5,6-dihydro-2H-[1]-benzothiepino[5,4-b]pyran-2-ones, generally in excellent yield.     

Characterization of the Trans-Epithelial Transport of Green Tea (C. sinensis) Catechin Extracts with In Vitro Inhibitory Effect against the SARS-CoV-2 Papain-like Protease Activity

This work describes an untargeted analytical approach for the screening, identification, and characterization of the trans-epithelial transport of green tea (Camellia sinensis) catechin extracts with in vitro inhibitory effect against the SARS-CoV-2 papain-like protease (PLpro) activity. After specific catechin extraction, a chromatographic separation obtained six fractions were carried out. The fractions were assessed in vitro against the PLpro target. Fraction 5 showed the highest inhibitory activity against the SARS-CoV-2 PLpro (IC₅₀ of 0.125 μg mL⁻¹). The untargeted characterization revealed that (−)-epicatechin-3-gallate (ECG) was the most abundant compound in the fraction and the primary molecule absorbed by differentiated Caco-2 cells. Results indicated that fraction 5 was approximately 10 times more active than ECG (IC₅₀ value equal to 11.62 ± 0.47 μg mL⁻¹) to inhibit the PLpro target. Overall, our findings highlight the synergistic effects of the various components of the crude extract compared to isolated ECG.     

Understanding the Effects of Crosslinking and Reinforcement Agents on the Performance and Durability of Biopolymer Films for Cultural Heritage Protection

In the last two decades, the naturally occurring polysaccharides, such as chitosan and pectin, have gained great attention having potential applications in different sectors, from biomedical to new generation packaging. Currently, the chitosan and pectic have been proposed as suitable materials also for the formulation of films and coatings for cultural heritage protection, as well as packaging films. Therefore, the formulation of biopolymer films, considering only naturally occurring polymers and additives, is a current challenging trend. This work reports on the formulation of chitosan (CS), pectin (PC), and chitosan:pectin (CS:PC) films, also containing natural crosslinking and reinforcement agents, such as citric acid (CA) and halloysite nanotubes (HNT), through the solvent casting technique. The produced films are characterized through water contact angle measurements, infrared and UV–visible spectroscopy and tensile test, while the durability of the CS:PC films is evaluated subjecting the film to accelerated UVB exposure and monitoring the photo-oxidation degradation in time though infrared spectroscopy. All obtained results suggest that both crosslinking and reinforcement agents have beneficial effects on the wettability, rigidity, and photo-oxidation resistance of biopolymer films. Therefore, these biopolymer films, also containing naturally occurring additives, have good properties and performance and they are suitable as coverage films for cultural heritage protection.     

Synthesis of Platinum(II) N-Heterocyclic Carbenes Based on Adenosine

Organometallic derivatization of nucleosides is a highly promising strategy for the improvement of the therapeutic profile of nucleosides. Herein, a methodology for the synthesis of metalated adenosine with a deprotected ribose moiety is described. Platinum(II) N-heterocyclic carbene complexes based on adenosine were synthesized, namely N-heterocyclic carbenes bearing a protected and unprotected ribose ring. Reaction of the 8-bromo-2′,3′,5′-tri-O-acetyladenosine with Pt(PPh₃)₄ by C8−Br oxidative addition yielded complex 1, with a Pt^II centre bonded to C-8 and an unprotonated N7. Complex 1 reacted at N7 with HBF₄ or methyl iodide, yielding protic carbene 2 or methyl carbene 3, respectively. Deprotection of 1 to yield 4 was achieved with NH₄OH. Deprotected compound 4 reacted at N7 with HCl solutions to yield protic NHC 5 or with methyl iodide yielding methyl carbene 6. Protic N-heterocyclic carbene 5 is not stable in DMSO solutions leading to the formation of compound 7, in which a bromide was replaced by chloride. The cis-influence of complexes 1–7 was examined by ³¹P{¹H} and ¹⁹⁵Pt NMR. Complexes 2, 3, 5, 6 and 7 induce a decrease of ¹J_Pt,P of more than 300 Hz, as result of the higher cis-influence of the N-heterocyclic carbene when compared to the azolato ligand in 1 and 4.     

Toxics or Lures? Biological and Behavioral Effects of Plant Essential Oils on Tephritidae Fruit Flies

The family Tephritidae (Diptera) includes species that are highly invasive and harmful to crops. Due to globalization, international trade, and human displacement, their spread is continuously increasing. Unfortunately, the control of tephritid flies is still closely linked to the use of synthetic insecticides, which are responsible for detrimental effects on the environment and human health. Recently, research is looking for alternative and more eco-friendly tools to be adopted in Integrated Pest Management (IPM) programs. In this regard, essential oils (EOs) and their main compounds represent a promising alternative to chemical insecticides. EOs are made up of phytoconstituents formed from the secondary metabolism of many plants and can act as attractants or toxics, depending on the dose. Because of this unique characteristic, EOs and their main constituents are promising tools that can be used both in Sterile Insect Technique (SIT) programs and in the “lure and kill” technique, exploiting the attractiveness of the product in the former case and its toxicity in the latter. In this article, current knowledge on the biological and behavioral effects of EOs and their main constituents on tephritid fruit flies is reviewed, mainly focusing on species belonging to the Anastrepha, Bactrocera, Ceratitis, and Zeugodacus genera. The mechanisms of action of EOs, their real-world applications, and challenges related to their use in IPM are critically discussed.     

Evaluation of 3- and 4-Phenoxybenzamides as Selective Inhibitors of the Mono-ADP-Ribosyltransferase PARP10

Intracellular ADP-ribosyltransferases catalyze mono- and poly-ADP-ribosylation and affect a broad range of biological processes. The mono-ADP-ribosyltransferase PARP10 is involved in signaling and DNA repair. Previous studies identified OUL35 as a selective, cell permeable inhibitor of PARP10. We have further explored the chemical space of OUL35 by synthesizing and investigating structurally related analogs. Key synthetic steps were metal-catalyzed cross-couplings and functional group modifications. We identified 4-(4-cyanophenoxy)benzamide and 3-(4-carbamoylphenoxy)benzamide as PARP10 inhibitors with distinct selectivities. Both compounds were cell permeable and interfered with PARP10 toxicity. Moreover, both revealed some inhibition of PARP2 but not PARP1, unlike clinically used PARP inhibitors, which typically inhibit both enzymes. Using crystallography and molecular modeling the binding of the compounds to different ADP-ribosyltransferases was explored regarding selectivity. Together, these studies define additional compounds that interfere with PARP10 function and thus expand our repertoire of inhibitors to further optimize selectivity and potency.