Contrasted effect of CO on the metal‐catalyzed cycloisomerization of O‐tethered enynes derived from monoterpenes

The CO‐bubbling effect in cycloisomerization reactions of enynes derived from monoterpenes has been studied using PtCl₂, [Rh₂Cl₂(CO)₄] and AuCl₃ as catalytic systems. All the precursors are efficient catalysts for the cycloisomerization of O‐tethered enynes. The reaction proceeds through exo‐dig and endo‐dig pathways, which are consistent with the exclusive coordination of the alkyne triple bond to the metal center. The CO ligand not only increases the reaction rates but also induces significant variations in the two reaction pathways. Notably, this effect is also strongly dependent on the nature of the starting enyne. Copyright © 2011 John Wiley & Sons, Ltd.     

A Facile and Cost‐effective Electroanalytical Strategy for the Quantification of Deoxyguanosine and Deoxyadenosine in Oligonucleotides Using Screen‐printed Graphite Electrodes

The development of electroanalytical methods for the detection and quantification of nucleotides in DNA offers vital implications in assessing the degree of oxidation or epigenetic modification in DNA. Unfortunately, the electrochemical response of oligonucleotides is strongly influenced by the size, composition and nucleic base sequence. In this article, an optimized analytical procedure for the enzymatically breakdown of the oligonucleotides to their corresponding nucleotides for the evaluation of the electrochemical response through the use of square wave voltammetry (SWV) is presented. Enzymatic digestion of oligonucleotides has been optimized in terms of buffer composition, digestion time, strategy for stopping the enzymatic reaction and filtration requirement for enzyme removal, and then compared to an established protocol. Under the optimized protocol SWV response of a number of untreated and enzymatically digested six‐mer oligonucleotides, namely 5′‐GGGGGG‐3′, 5′‐AAAAAA‐3′, 5′‐CGCGCG‐3′ and 5′‐AAACGC‐3′ have been analysed, providing a higher sensitivity for the determination of guanosine and adenosine monophosphate species under digestion conditions with a more facile and cost effective procedure. The novel strategy for the enzymatically treated oligonucleotides in combination with the SWV response provides a proof of principle for feasible applications in the diagnosis of methylated guanosine in DNA as a potential biomarker due to its relation with cancer.     

Stepwise sequential redox potential modulation possible on a single platform

Step by step: The cluster [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) is an excellent platform for making a stepwise tunable redox potential system by dehydroiodination. With the addition of up to eight iodine substituents (purple; see picture), there is a fall in the E(1/2)(Co(III)/Co(II)) value from -1.80?V to -0.68?V (vs. Fc(+)/Fc; Fc = ferrocene). A practical application of this tunability has been observed in the growth of polypyrrole.     

1H and 13C NMR spectral assignment of androstane derivatives

(1)H and (13)C NMR spectroscopic data for 5alpha-androstanes and halo-5alpha-androstanes with different substituents at positions C-3, C-9, C-11 and C-17 were examined and assigned by a combination of 1D and 2D NMR experiments. The substituent effects on the (13)C chemical shifts were compared with those of epi-androsterone, used as a reference compound. The coupling constants (n)J((19)F,(13)C) were measured for compounds 6, 8, 11 and 14.     

Giant Volume Change and Topological Gaps in Temperature‐ and Pressure‐Induced Phase Transitions: Experimental and Computational Study of ThMo2O8

By applying high temperature (1270 K) and high pressure (3.5 GPa), significant changes occur in the structural volume and crystal topology of ThMo₂O₈, allowing the formation of an unexpected new ThMo₂O₈ polymorph (high‐temperature/high‐pressure (HT/HP) orthorhombic ThMo₂O₈). Compared with the other three ThMo₂O₈ polymorphs prepared at the ambient pressure (monoclinic, orthorhombic, and hexagonal phases), the molar volume for the quenched HT/HP–orthorhombic ThMo₂O₈ is decreased by almost 20 %. As a result of such a dramatic structural transformation, a permanent high‐pressure quenchable state is able to be sustained when the pressure is released. The crystal structures of the three ambient ThMo₂O₈ phases are based on three‐dimensional (3D) frameworks constructed from corner‐sharing ThO_x (x=6, 8, or 9) polyhedra and MoO₄ tetrahedra. The HT/HP–orthorhombic ThMo₂O₈, however, crystallizes in a novel structural topology, exhibiting very dense arrangements of ThO₁₁ and MoO₄₊₁ polyhedra connecting along the crystallographic c axis. The phase transitions among all four of these ThMo₂O₈ polymorphs are unveiled and fully characterized with regard to the structural transformation, thermal stability, and vibrational properties. The complementary first principles calculations of Gibbs free energies reveal the underlying energetics of the phase transition, which support the experimental findings.     

Parameter estimation of a nonlinear magnetic universe from observations

The cosmological model consisting of a nonlinear magnetic field obeying the Lagrangian \(\mathcal {L}= \gamma F^{\alpha },\, F\) being the electromagnetic invariant, coupled to a Robertson-Walker geometry is tested with observational data of Type Ia Supernovae, Long Gamma-Ray Bursts and Hubble parameter measurements. The statistical analysis show that the inclusion of nonlinear electromagnetic matter is enough to produce the observed accelerated expansion, with not need of including a dark energy component. The electromagnetic matter with abundance \(\varOmega _B\) , gives as best fit from the combination of all observational data sets \(\varOmega _B=0.562^{+0.037}_{-0.038}\) for the scenario in which \(\alpha =-1, \varOmega _B=0.654^{+0.040}_{-0.040}\) for the scenario with \(\alpha =-1/4\) and \(\varOmega _B=0.683^{+0.039}_{-0.043}\) for the one with \(\alpha =-1/8\) . These results indicate that nonlinear electromagnetic matter could play the role of dark energy, with the theoretical advantage of being a mensurable field.     

Different cell death mechanisms are induced by a hydrophobic flavin in human tumor cells after visible light irradiation

Riboflavin (RF) is an endogenous cell component and an efficient photosensitizer that can act by both types I and II photochemical mechanisms. Human tumor cells lines cultured in vitro, were used as model to study the effect of a photosensitizer synthesized from riboflavin, the 2',3',4',5'-riboflavin-tetrabutyrate (RTB), to increase the flavin concentration in the human promyelocytic leukemia cell line HL-60 and the human epithelial cervical cancer cell line HeLa. We demonstrate that this compound, alone or with Trp, has a toxic dose-response effect evidenced by abnormal cell morphology and a decrease in the cell proliferation rate. The mechanism of cell death was investigated and the experimental evidence indicates that it proceeds primarily via apoptosis; however, autophagy cannot be discarded. Nuclear fluorescent staining with Hoechst 33258 and transmission electron microscopy of the cells showed condensed chromatin margination at the nuclear periphery and the formation of apoptotic bodies. Furthermore, Caspase-3 activity was demonstrated in both cell lines. In addition, the characteristic apoptotic DNA ladder was observed in HL-60 cells. On the other hand, a high cytoplasmic vacuolization was observed by electron transmission and confocal microscopy. LysoTraker-red localization in the vacuoles was observed by fluorescence microscopy, and a significant decrease in the number of vacuoles and in the cell proliferation rate diminution was observed when irradiation was performed in the presence of the autophagy inhibitor 3-methyladenine. Considering that both cell death mechanisms have a dual role in the killing of tumor cells in vivo, a harmful effect that does not cause inflammation leading to tumor prophylaxis, we conclude that RTB could have potential clinical applications.