Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300{\deg}C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO-LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure.Comment: 9 pages, 6 figure

Fabrication of a label-free electrochemical immunosensor using a redox active ferrocenyl dendrimer

We report an IgG (=immunoglobulin) electrochemical immunosensor using a newly synthesized redox-active ferrocenyl dendrimer of generation 2 (G2Fc) as a voltammetric transducer. The ferrocenyl dendrimer N(CH2CH2C(O)NHCH2CH2NHC(O)Fe(η5-C5H4)(η5-C5H5))(CH2CH2N(CH2CH2C(O)NHCH2CH2NHC(O)Fe(η5-C5H4)(η5-C5H5))2)2 (G2Fc) was used as a functional moiety to immobilize the antibody on the surface of the electrode. A sandwich immunosensor of the type IgG/Bovine serum albumin (BSA)/anti-IgG/G2Fc/glassy carbon electrode (GCE) was fabricated. The electrochemical properties of G2Fc were thoroughly studied in aqueous and non-aqueous electrolytes with varying scan rates. The incubation time was optimized for better analytical performance of the immunosensor. It is found that the developed amperometric immunosensor is sensitive to a concentration of IgG as low as 2 ng mL−1.Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

A model of partial differential equations for HIV propagation in lymph nodes

Texto completo versión postprint de autor.-- PACS numbers: 02.30.Ks,02.30.Hq,87.18.Hf,87.19.XxA system of partial differential equations is used to model the dissemination of the Human Immunodeficiency Virus (HIV) in CD4+T cells within lymph nodes. Besides diffusion terms, the model also includes a time-delay dependence to describe the time lag required by the immunologic system to provide defenses to new virus strains. The resulting dynamics strongly depends on the properties of the invariant sets of the model, consisting of three fixed points related to the time independent and spatial homogeneous tissue configurations in healthy and infected states. A region in the parameter space is considered, for which the time dependence of the space averaged model variables follows the clinical pattern reported for infected patients: a short scale primary infection, followed by a long latency period of almost complete recovery and third phase characterized by damped oscillations around a value with large HIV counting. Depending on the value of the diffusion coefficient, the latency time increases with respect to that one obtained for the space homogeneous version of the model. It is found that same initial conditions lead to quite different spatial patterns, which depend strongly on the latency interval.This work was partially supported by the following Brazilian funding agencies: CAPES, FAPESB/PRONEX, CNPq and National Institute for Science and Technology/Complex Systems.Peer reviewe

Modeling Dual Pathways for the Metazoan Spindle Assembly Checkpoint

Using computational modelling, we investigate mechanisms of signal transduction focusing on the spindle assembly checkpoint where a single unattached kinetochore is able to signal to prevent cell cycle progression. This inhibitory signal switches off rapidly once spindle microtubules have attached to all kinetochores. This requirement tightly constrains the possible mechanisms. Here we investigate two possible mechanisms for spindle checkpoint operation in metazoan cells, both supported by recent experiments. The first involves the free diffusion and sequestration of cell-cycle regulators. This mechanism is severely constrained both by experimental fluorescence recovery data and also by the large volumes involved in open mitosis in metazoan cells. Using a simple mathematical analysis and computer simulation, we find that this mechanism can generate the inhibition found in experiment but likely requires a two stage signal amplification cascade. The second mechanism involves spatial gradients of a short-lived inhibitory signal that propagates first by diffusion but then primarily via active transport along spindle microtubules. We propose that both mechanisms may be operative in the metazoan spindle assembly checkpoint, with either able to trigger anaphase onset even without support from the other pathway.Comment: 9 pages, 2 figure

A Difference Version of Nori's Theorem

We consider (Frobenius) difference equations over (F_q(s,t), phi) where phi fixes t and acts on F_q(s) as the Frobenius endomorphism. We prove that every semisimple, simply-connected linear algebraic group G defined over F_q can be realized as a difference Galois group over F_{q^i}(s,t) for some i in N. The proof uses upper and lower bounds on the Galois group scheme of a Frobenius difference equation that are developed in this paper. The result can be seen as a difference analogue of Nori's Theorem which states that G(F_q) occurs as (finite) Galois group over F_q(s).Comment: 29 page

Combining chromomagnetic and four-fermion operators with leading SMEFT operators for gg→hhgg\to hh at NLO QCD

We present the calculation of the contribtuions from the chromomagnetic and four-top-quark-operators within Standard Model Effective Field Theory (SMEFT) to Higgs boson pair production in gluon fusion, combined with full NLO QCD corrections. We study the effects of these operators on the total cross section and the invariant mass distribution of the Higgs-boson pair, at $\sqrt{s}=13.6$ TeV. These subleading operators are implemented in the generator ggHH_SMEFT, in the same Powheg-Box-V2 framework as the leading operators, such that their effects can be easily studied in a unified setup.Comment: 35 pages, 11 figure