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A new Morita-Baylis-Hillman Adduct (MBHA) derivative 7 was designed and synthesized to obtain a reactive molecule potentially capable of labelling basic amino acid residues. Compound 7 was easily prepared and characterized from the point of view of its photophysical and photochemical features before then to be used in labelling experiments with amino acid. [Display omitted] • A new Morita-Baylis-Hillman derivative was designed to obtain a reactive molecule capable of labelling basic amino acids. • This compound was promptly synthesized in three steps from commercially available intermediates. • This compound showed an intriguing photochemical activity, which was characterized by photophysical and NMR studies. • These results pave the way for the use of the derivative in the fluorogenic labeling of proteins. [ABSTRACT FROM AUTHOR]

• 2-Pyr- BF3a organizes into a crystalline solid-state without spontaneous polymerization. • Photopolymerization occurs in amorphous films, but not in solution or in crystals. • The polymer shows a more intense emission in solution than in the solid state. Benzofulvene derivative 2-Pyr- BF3a was designed and synthesized to evaluate the effects of a pyridine ring in position 2 of the 3-phenylbenzofulvene moiety on the spontaneous solid-state polymerization. The monomer was found to organize into an ordered crystalline solid-state without significant spontaneous polymerization, but the irradiation of amorphous film samples with UV-light produced photopolymerization. Resulting poly-2-Pyr- BF3a was characterized by NMR spectroscopy, MALDI-TOF mass spectrometry, and photophysical studies in comparison with the corresponding monomer. Interestingly, monomer 2-Pyr- BF3a was weakly emissive in diluted solutions, but increased its PLQY in the crystalline solid. Conversely, after photopolymerization the monomeric unit in the polymer enhanced its emission intensity in solution while in the solid state results weakly emissive. Even more interestingly, this benzofulvene monomer and its synthetic precursors 2 and 3 showed long-lived emission suggesting a phosphorescence nature of the emission process. Finally, DFT and TDDFT calculations were performed in order to rationalize the experimental data. [ABSTRACT FROM AUTHOR]

Spontaneous polymerization is an intriguing phenomenon in which pure monomers begin their polymerization without initiators or catalysts. Previously, 3-phenylbenzofulvene monomers were found to polymerize spontaneously after solvent removal. Here, eight new 3-substituted benzofulvene monomers 1a–h were synthesized in order to investigate the effects of differently substituted aromatic rings in position 3 of the benzofulvene scaffold on spontaneous polymerization. The newly synthesized monomers maintained the tendency toward spontaneous polymerization. However, monomer 1a, bearing an ortho-methoxy substituted phenyl, polymerized hardly, thus producing low polymerization yields, inhomogeneous structure, and low molecular weight of the obtained polymeric material. This result suggested the importance of the presence of hydrogen atoms in the 2′-position to achieve productive interactions among the monomers in the recognition step preluding the spontaneous polymerization and among the monomeric units in the polybenzofulvene backbones. Moreover, this study paves the way to modify the pendant rings in position 3 of the indene scaffold to synthesize new polybenzofulvene derivatives variously decorated. [ABSTRACT FROM AUTHOR]

The design of compounds able to combine the selective inhibition of cyclooxygenase-2 (COX-2) with the release of nitric oxide (NO) is a promising strategy to achieve potent anti-inflammatory agents endowed with an overall safer profile and reduced toxicity upon gastrointestinal and cardiovascular systems. With the aim of generating novel and selective COX-2 inhibiting NO-donors (CINOD) and encouraged by the promising results obtained with our nitrooxy- and hydroxyethyl ethers 11 and 12 reported in previous works, we shifted our attention on the synthesis of isosteric thioanalogs nitrooxy- and hydroxy ethyl sulfides 13a-c and 14a-c, respectively, along with their oxidation products nitrooxy- and hydroxyethyl sulfoxides 15a-c and 16a-c, respectively, also referred to as thio-CINOD. Preliminary data and metabolic analysis highlighted how the isosteric substitution of the ethereal oxygen atom of 11a-c with sulfur in compounds 13a-c , independently from the presence and the number of fluorine atoms in N 1 -phenyl ring, leads to new selective and highly potent COX-2 inhibitors, capable to induce vasorelaxant responses in vivo. The same behavior is observed with their oxidized counterparts nitrooxyethyl sulfoxides 15a-c , in which the oxidation state of the sulfur atom and the presence of the additional oxygen atom play a substantial role in enhancing compounds activity and vasorelaxation. In addition, the screened compounds proved significantly efficacious in mouse models of inflammation and nociception at the dose of 20 mg/kg. [Display omitted] • Novel analgesic/anti-inflammatory agents 13 – 16 as dual selective COX-2 inhibitors containing a NO donor moiety were proposed. • SARs of target compounds 13 – 16 are carefully explored. • The isosteric O-to-S replacement led to selective and highly potent COX-2 inhibitors 13a-c and 15a-c. • Hydroxyethyl sulfides 14a-c also showed an efficacious and selective COX-2 inhibitory activity. • Compounds 13a-c and 15a-c , containing a NO donor moiety, showed intriguing vasorelaxant properties. [ABSTRACT FROM AUTHOR]