Visible Light and Triselenium Dicyanide (TSD): New Horizons in the Synthesis of Organic Selenocyanates.

Herein, we describe a new method for the synthesis of α-carbonyl selenocyanates by reacting triselenium dicyanide (TSD) and styrenes under blue light irradiation and O2 atmosphere. The reactions are triggered by the formation of Se-centered radical species, followed by the addition/oxidation of the styrene π-bond. α-Carbonyl selenocyanates and α-hydroxy selenocyanates were obtained in moderate to excellent yields from aryl- and alkyl-substituted alkenes, respectively. It was demonstrated that α-carbonyl selenocyanates could be used as a synthetic platform in a multicomponent reaction strategy to prepare 2-phenylimidazo[1,2-a]pyridine derivatives, which were evaluated for their photophysical properties. Overall, this new method provides a useful tool for synthesizing α-carbonyl selenocyanates, and demonstrates their potential for use in the synthesis of other compounds, thus giving new synthetic opportunities to construct organic selenocyanate compounds.

Large Telluroxane Bowls Connected by a Layer of Iodine Ions.

Phenyltelluroxane clusters of the composition [{(PhTe)19 O24 }2 I18 (solv)] (1) are formed during the hydrolysis of [PhTeI3 ]2 or the oxidation of various phenyltellurium(II) compounds with iodine under hydrolytic conditions. The compounds consist of two half-spheres with a {(PhTe)19 O24 }9+ network, which are connected by 18 iodine atoms. The spherical clusters can accommodate solvent molecules such as pyridine or methanol in the center of two rings formed by iodine atoms. The presence of other metal ions during the cluster formation results in a selective replacement of the central {PhTe}3+ units of each half-sphere as has been demonstrated with the isolation of [{(PhTe)18 ({Ca(H2 O)2 }O24 }2 I16 ] (2) and [{(PhTe)18 ({Y(NO3 )(H2 O)}O24 }2 I16 ] (3). A crownether-like coordination by six oxygen atoms of the telluroxane network is found for the {Ca(H2 O}2 }2+ and {Y(NO3 )(H2 O)}2+ building blocks. Mass spectrometric studies show that considerable amounts of the intact clusters are transferred to the gas phase without dissociation.

Theoretical study of C6F5-corrole molecules functionalized with aromatic groups for Photodynamic Therapy.

The singlet oxygen generation by electronically excited molecules in photodynamic therapy (PDT) requires light absorption within a specific wavelength window, and a subsequent intersystem crossing transition to a triplet excited state that is, at least, 0.98 eV higher in energy than the singlet ground state. Tetrapyrrolic macrocycles, such as porphyrin and corrole, have been widely used in oxygen singlet generation for PDT. Suitable functionalization can potentialize these macrocycles as photosensitizers. In this contribution, we use Density Functional Theory (DFT) calculations to determine the structural, electronic and spectroscopic properties of corrole macrocycles bound to different polycyclic aromatic groups in the gas phase, dichloromethane, and water. We also calculate the spin-orbit coupling (SOC) matrix elements of the intersystem crossing channels involving the first excited singlet states and excited triplet states. The results for optical absorption show that the threshold wavelength for optical absorption increases with the polarity of the environment and the number of aromatic rings of the ligands, whereas the oscillator strengths increase with the polarity of the environment but decrease with the number of aromatic rings. It is verified that the triplet excited states involved in the intersystem crossing transitions satisfy the energy requirement for the oxygen singlet generation. The magnitude of spin-orbit coupling (SOC) matrix elements associated with the intersystem crossing are also seen to be dependent on the environment involving the corrole molecules, and on the number of aromatic rings of the ligands connected to the corrole. Further, the binding of the functionalized corrole molecules with biomolecules as the calf thymus DNA and human serum albumin is studied and characterized through molecular docking. These results show that the corrole macrocycles, suitably functionalized with polycyclic aromatic groups, fulfill several criteria to be considered as good PDT photosensitizers.

Methylmercury's chemistry: From the environment to the mammalian brain.

Methylmercury is a neurotoxicant that is found in fish and rice. MeHg's toxicity is mediated by blockage of -SH and -SeH groups of proteins. However, the identification of MeHg's targets is elusive. Here we focus on the chemistry of MeHg in the abiotic and biotic environment. The toxicological chemistry of MeHg is complex in metazoans, but at the atomic level it can be explained by exchange reactions of MeHg bound to -S(e)H with another free -S(e)H group (R1S(e)-HgMe + R2-S(e)H ↔ R1S(e)H + R2-S(e)-HgMe). This reaction was first studied by professor Rabenstein and here it is referred as the "Rabenstein's Reaction". The absorption, distribution, and excretion of MeHg in the environment and in the body of animals will be dictated by Rabenstein's reactions. The affinity of MeHg by thiol and selenol groups and the exchange of MeHg by Rabenstein's Reaction (which is a diffusion controlled reaction) dictates MeHg's neurotoxicity. However, it is important to emphasize that the MeHg exchange reaction velocity with different types of thiol- and selenol-containing proteins will also depend on protein-specific structural and thermodynamical factors. New experimental approaches and detailed studies about the Rabenstein's reaction between MeHg with low molecular mass thiol (LMM-SH) molecules (cysteine, GSH, acetyl-CoA, lipoate, homocysteine) with abundant high molecular mass thiol (HMM-SH) molecules (albumin, hemoglobin) and HMM-SeH (GPxs, Selenoprotein P, TrxR1-3) are needed. The study of MeHg migration from -S(e)-Hg- bonds to free -S(e)H groups (Rabenstein's Reaction) in pure chemical systems and neural cells (with special emphasis to the LMM-SH and HMM-S(e)H molecules cited above) will be critical to developing realistic constants to be used in silico models that will predict the distribution of MeHg in humans.