Tetrapyrrole singlet excited state quenching by carotenoids in an artificial photosynthetic antenna

Two artificial photosynthetic antenna models consisting of a Si phthalocyanine (Pc) bearing two axially attached carotenoid moieties having either 9 or 10 conjugated double bonds are used to illustrate some of the function of carotenoids in photosynthetic membranes. Both models studied in toluene, methyltetrahydrofuran, and benzonitrile exhibited charge separated states of the type C*+-Pc*- confirming that the quenching of the Pc S1 state is due to photoinduced electron transfer. In hexane, the Pc S1 state of the 10 double bond carotenoid-Pc model was slightly quenched but the C*+-Pc*- transient was not spectroscopically detected. A semiclassical analysis of the data in hexane at temperatures ranging from 180 to 320 K was used to demonstrate that photoinduced electron transfer could occur. The model bearing the 10 double bond carotenoids exhibits biexponential fluorescence decay in toluene and in hexane, which is interpreted in terms of an equilibrium mixture of two isomers comprising s-cis and s-trans conformers of the carotenoid. The shorter fluorescence lifetime is associated with an s-cis carotenoid conformer where the close approach between the donor and acceptor moieties provides through-space electronic coupling in addition to the through-bond component.     

Cyclotetraveratrylene and its benzene solvate

The title compound crystallizes in a solvent-free form and also includes solvent molecules. The X-ray structure analysis reveals that in the both crystal forms the cyclododecatetraene ring in the host molecules adopts a sofa conformation. The guest molecules occupy the channels formed among columns of stacked host molecules.Contribution No. 1452 of Instituto de Química, UNAM.     

The Mechanical and Biological Performance of Photopolymerized Gelatin-Based Hydrogels as a Function of the Reaction Media

From the first experiments with biomaterials to mimic tissue properties, the mechanical and biochemical characterization has evolved extensively. Several properties can be described, however, what should be essential is to conduct a proper and physiologically relevant characterization. Herein, the influence of the reaction media (RM) and swelling media (SM)–phosphate buffered saline (PBS) and Dulbecco's modified Eagle's medium (DMEM) with two different glucose concentrations–is described in gelatin methacrylamide (GelMA) hydrogel mechanics and in the biological behavior of two tumoral cell lines (Caco-2 and HCT-116). All scaffolds are UV-photocrosslinked under identical conditions and evaluated for mass swelling ratio and stiffness. The results indicate that stiffness is highly susceptible to the RM, but not to the SM. Additionally, PBS-prepared hydrogels exhibited a higher photopolymerization degree according to high resolution magic-angle spinning (HR-MAS) NMR. These findings correlate with the biological response of Caco-2 and HCT-116 cells seeded on the substrates, which demonstrated flatter morphologies on stiffer hydrogels. Overall, cell viability and proliferation are excellent for both cell lines, and Caco-2 cells displayed a characteristic apical-basal polarization based on F-actin/Nuclei fluorescence images. These characterization experiments highlight the importance of conducting mechanical testing of biomaterials in the same medium as cell culture.     

The Role of Mechanical Properties and Structure of Type I Collagen Hydrogels on Colorectal Cancer Cell Migration

Mechanical interactions between cells and their microenvironment play an important role in determining cell fate, which is particularly relevant in metastasis, a process where cells invade tissue matrices with different mechanical properties. In vitro, type I collagen hydrogels have been commonly used for modeling the microenvironment due to its ubiquity in the human body. In this work, the combined influence of the stiffness of these hydrogels and their ultrastructure on the migration patterns of HCT-116 and HT-29 spheroids are analyzed. For this, six different types of pure type I collagen hydrogels by changing the collagen concentration and the gelation temperature are prepared. The stiffness of each sample is measured and its ultrastructure is characterized. Cell migration studies are then performed by seeding the spheroids in three different spatial conditions. It is shown that changes in the aforementioned parameters lead to differences in the mechanical stiffness of the matrices as well as the ultrastructure. These differences, in turn, lead to distinct cell migration patterns of HCT-116 and HT-29 spheroids in either of the spatial conditions tested. Based on these results, it is concluded that the stiffness and the ultrastructural organization of the matrix can actively modulate cell migration behavior in colorectal cancer spheroids.     

Topological crossovers in the forced folding of self-avoiding matter

We study the scaling properties of forced folding of thin materials of different geometry. The scaling relations implying the topological crossovers from the folding of three-dimensional plates to the folding of two-dimensional sheets, and further to the packing of one-dimensional strings, are derived for elastic and plastic manifolds. These topological crossovers in the folding of plastic manifolds were observed in experiments with predominantly plastic aluminum strips of different geometry. Elasto-plastic materials, such as paper sheets during the (fast) folding under increasing confinement force, are expected to obey the scaling force-diameter relation derived for elastic manifolds. However, in experiments with paper strips of different geometry, we observed the crossover from packing of one-dimensional strings to folding two dimensional sheets only, because the fractal dimension of the set of folded elasto-plastic sheets is the thickness dependent due to the strain relaxation after a confinement force is withdrawn.     

<Emphasis Type="Italic">Z</Emphasis><Superscript>′</Superscript> boson signal at Fermilab-Tevatron and CERN-LHC in a 331 model

We analyse the possibilities to detect a new Z ^′ boson in di-electron events at Tevatron and LHC in the framework of the 331 model with right-handed neutrinos. We also study other fermions and Higgs events as final state at LHC. Using collision data collected by the CDF II detector at Fermilab Tevatron, we find that the 331 Z ^′ boson is excluded with masses below 920 GeV. For an integrated luminosity of 100 fb⁻¹ at LHC, and considering a central value GeV, we obtain the invariant-mass distribution in the process pp→Z ^′→e ⁺ e ⁻, where a huge peak, corresponding to 800 signal events/(20 GeV), is found above the SM background. The number of di-electron events vary from 50000 to 2400 in the mass range of –2000 GeV. We also obtain branching ratios and cross sections in other fermion and Higgs channels at LHC, where a heavy top quark T exhibits the biggest ratio with m _T =300 GeV.