Influence of CF3 Substituents on the Spin Crossover Behavior of Iron(II) Coordination Polymers with Schiff Base-like Ligands

A Schiff base-like ligand bearing CF₃ substituents was synthesized and converted to iron(II) coordination polymers [{FeL(L_ax)}_n] using five different bridging ligands L_ax. The structure of the coordination polymers was investigated using powder X-ray diffraction and single-crystal X-ray diffraction in the case of [{FeL(bipy)}_n]. The later revealed an untypical ABAB pattern of alternating equatorial ligands rotated by 180° with regard to each other along the chain. The temperature-dependent magnetic behavior was investigated with a SQUID magnetometer and the spin states at room temperature were confirmed by ⁵⁷Fe-Mössbauer spectroscopy. Three out of five coordination polymers show spin crossover behavior in the temperature range between 50 and 400 K with different kind of curve progressions (abrupt, gradual, step-wise). The other two coordination polymers are either fully highspin or fully low spin.     

Intracellular Ruthenium‐Promoted (2+2+2) Cycloadditions

Metal‐mediated intracellular reactions are becoming invaluable tools in chemical and cell biology, and hold promise for strongly impacting the field of biomedicine. Most of the reactions reported so far involve either uncaging or redox processes. Demonstrated here for the first time is the viability of performing multicomponent alkyne cycloaromatizations inside live mammalian cells using ruthenium catalysts. Both fully intramolecular and intermolecular cycloadditions of diynes with alkynes are feasible, the latter providing an intracellular synthesis of appealing anthraquinones. The power of the approach is further demonstrated by generating anthraquinone AIEgens (AIE=aggregation induced emission) that otherwise do not go inside cells, and by modifying the intracellular distribution of the products by simply varying the type of ruthenium complex.     

Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases

The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed.     

Single Higgs-boson production at a photon-photon collider: General 2HDM versus MSSM

We revisit the production of a single Higgs boson from direct γγ-scattering at a photon collider. We compute the total cross-section σ(γγ→h) (for h=h⁰,H⁰,A⁰), and the strength of the effective gh⁰γγ coupling normalized to the Standard Model (SM), for both the general Two-Higgs-Doublet Model (2HDM) and the Minimal Supersymmetric Standard Model (MSSM). In both cases the predicted production rates for the CP-even (odd) states render up to 10⁴ (10³) events per 500 fb⁻¹ of integrated luminosity, in full consistency with all the theoretical and phenomenological constraints. Depending on the channel the maximum rates can be larger or smaller than the SM expectations, but in most of the parameter space they should be well measurable. We analyze how these departures depend on the dynamics underlying each of the models, supersymmetric and non-supersymmetric, and highlight the possible distinctive phenomenological signatures. We demonstrate that this process could be extremely useful to discern non-supersymmetric Higgs bosons from supersymmetric ones. Furthermore, in the MSSM case, we show that γγ-physics could decisively help to overcome the serious impasse afflicting Higgs boson physics at the infamous “LHC wedge”.     

and applications

We study an analogue of the classical theory of weights in without assuming that the underlying measure is doubling. Then, we obtain weighted norm inequalities for the (centered) Hardy-Littlewood maximal function and corresponding weighted estimates for nonclassical Calderón-Zygmund operators. We also consider commutators of those Calderón- Zygmund operators with bounded mean oscillation functions (), extending the main result from R. Coifman, R. Rochberg, and G. Weiss, Factorization theorems for Hardy spaces in several variables, Ann. of Math. 103 (1976), 611-635. Finally, we study self-improving properties of Poincaré-B.M.O. type inequalities within this context; more precisely, we show that if is a locally integrable function satisfying for all cubes , then it is possible to deduce a higher integrability result for , assuming a certain simple geometric condition on the functional .     

Synthesis and characterization of [Cu(Me2oxpn)Ni(NO2)(tmen)](ClO4): a single ferrimagnetic dinuclear CuII-NiII complex acting as weak molecule-based magnet

The new heterodinuclear complex [Cu(Me2oxpn)Ni(NO2)(tmen)](ClO4), that exhibits strong antiferromagnetic intramolecular coupling between CuII and NiII ions (ferrimagnetic behavior), shows ferromagnetic ordering at low temperature, due likely to a small canting phenomenon; it is one of the very few compounds made from isolated molecules that lead to cooperative magnetic behavior.     

Direct H atom abstraction from spore photoproduct C-6 initiates DNA repair in the reaction catalyzed by spore photoproduct lyase: evidence for a reversibly generated adenosyl radical intermediate

Spore photoproduct (SP) lyase, which catalyzes the direct reversal of SP (5-thyminyl-5,6-dihydrothymine) to thymine monomers, is the only identified nonphotoactivatable pyrimidine dimer lyase. Unlike DNA photolyase, SP lyase does not contain a flavin cofactor and does not require light for activation. Instead, preliminary studies point to the presence of an iron-sulfur cluster in SP lyase and the requirement for S-adenosylmethionine (AdoMet) for catalytic activity, suggesting that SP lyase belongs to the growing group of iron-sulfur cluster and AdoMet-dependent radical enzymes. Here we provide evidence for the role of AdoMet as a reversible deoxyadenosyl radical generator, which initiates repair by hydrogen atom abstraction from C-6 of SP. Reaction of 6-(3)H-SP, but not methyl-(3)H-SP, with SP lyase and AdoMet results in transfer of (3)H to AdoMet, while no tritiated 5'-deoxyadenosine is observed. When 5'-tritiated AdoMet is used in the reaction with unlabeled SP, transfer of (3)H into the repaired thymine monomers is observed. These results point to the reversible generation of a 5'-deoxyadenosyl radical intermediate, which reacts directly with the DNA lesion to initiate a radical-mediated beta-scission. We also demonstrate that AdoMet is a catalytic cofactor that is not consumed during turnover. Together, these results support a novel radical-based mechanism for the repair of UV-induced DNA damage.