A Hyperbolic Non Distributive Algebra in 1 + 2 Dimensions

We introduce a non distributive algebra over the reals in 1 + 2 dimensions that contains the hyperbolic complex algebra ${\mathbb{H}_2}$ . The algebra has divisors of zero that can be avoided by introducing the necessary conditions. Under these conditions, the proposed addition and product operations satisfy group properties. More stringent restrictions sufficient to satisfy group properties separate the algebra in two subspaces. As an application, the composition of velocities in a deformed Lorentz metric is presented. In this approach, Minkowski light cones are deformed into light bipyramids.     

Formic acid catalyzed keto-enol tautomerizations for C2 and C3 enols: Implications in atmospheric and combustion chemistry

Enols are important species in atmospheric and combustion chemistry. However, their implications in these environments are not well established due to a lack of accurate rate constants and mechanisms to determine their fate. In this work, we investigate the formic acid catalyzed keto-enol tautomerizations converting vinyl alcohol, propen-2-ol and 1-propenol into acetaldehyde, acetone and propanal, respectively. High-level ab initio and multistructural torsional variational transition state theory calculations are performed with small-curvature tunneling corrections to obtain rate constants in the temperature range 200 K-3000 K. Tunneling is shown to be pronounced as a consequence of very narrow adiabatic potential energy curves, and indicates a need to revisit previous calculations. We show the implications of the studied reactions on the fate of enols under combustion relevant conditions by detailed kinetic modeling simulations. The yield of vinyl alcohol predicted by our calculated rate constants may be useful to lessen the underestimation of organic acids concentrations in current atmospheric models.     

Electronic Structure and Triplet–Triplet Energy Transfer in Artificial Photosynthetic Antennas

Three Pd(II) phthalocyanine–carotenoid dyads featuring chromophores linked by amide bonds were prepared in order to investigate the rate of triplet–triplet (T‐T) energy transfer from the tetrapyrrole to the covalently attached carotenoid as a function of the number of conjugated double bonds in the carotenoid. Carotenoids having 9, 10 and 11 conjugated double bonds were studied. Transient absorption measurements show that intersystem crossing in the Pd(II) phthalocyanine takes place in 10 ps in each case and that T‐T energy transfer occurs in 126, 81 and 132 ps in the dyads bearing 9, 10 and 11 double bond carotenoids, respectively. To identify the origin of this variation in T‐T energy transfer rates, density functional theory (DFT) was used to calculate the T‐T electronic coupling in the three dyads. According to the calculations, the primary reason for the observed T‐T energy transfer trend is larger T‐T electronic coupling between the tetrapyrrole and the 10‐double bond carotenoid. A methyl group adjacent to the amide linker that connects the Pd(II) phthalocyanine and the carotenoid in the 9 and 11‐double bond carotenoids is absent in the 10‐double bond carotenoid, and this difference alters its electronic structure to increase the coupling.     

Molecular Scaffolds as Double‐Targeting Agents For the Diagnosis and Treatment of Neuroblastoma

The selective delivery of therapeutic and imaging agents to tumoral cells has been postulated as one of the most important challenges in the nanomedicine field. Meta‐iodobenzilguanidine (MIBG) is widely used for the diagnosis of neuroblastoma (NB) due to its strong affinity for the norepinephrine transporter (NET), usually overexpressed on the membrane of malignant cells. Herein, a family of novel Y‐shaped scaffolds has been synthesized, which have structural analogues of MIBG covalently attached at each end of the Y‐structure. The cellular uptake capacity of these double‐targeting ligands has been evaluated in vitro and in vivo, yielding one specific Y‐shaped structure that is able to be engulfed by the malignant cells, and accumulates in the tumoral tissue, at significantly higher levels than the structure containing only one single targeting agent. This Y‐shaped ligand can provide a powerful tool for the current treatment and diagnosis of this disease.     

Hooking Together Sigmoidal Monomers into Supramolecular Polymers

Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.     

Determination of the spectral diffusion kernel of a protein by single-molecule spectroscopy

The spectral dynamics of individual bacterial light-harvesting-2 pigment-protein complexes have been studied at 1.4 K. The data provided the spectral diffusion kernel of the optical transitions of the embedded B800 bacteriochlorophyll a pigments. This kernel can be described by either a single Gaussian function or a superposition of Gaussian functions. Moreover, we found that the chromophores interact with two classes of TLSs that can be distinguished by their distance from the chromophore and are most likely located outside (class 1) and inside (class 2) the protein matrix.     

Ferromagnetic Josephson junction with precessing magnetization

The Josephson current in a diffusive superconductor-ferromagnet-superconductor junction with precessing magnetization is calculated within the quasiclassical theory of superconductivity. When the junction is phase biased, a stationary current (without ac component) can flow through it despite the nonequilibrium condition. A large critical current is predicted due to a dynamically induced long range triplet proximity effect. Such an effect could be observed in a conventional hybrid device close to the ferromagnetic resonance.     

Two-dimensional thermometry using temperature-induced line shifts of ZnO:Zn and ZnO:Ga fluorescence

Sensitive temperature-induced line shifts of the near-band-edge emission from ZnO:Ga and ZnO:Zn are investigated for two-dimensional (2D) thermometry with nanosecond time resolution. Spectral and temporal concerns for 2D measurements and the feasibility for utilizing the line shifts for temperature measurements using a spectral ratio are investigated. Owing to the high temperature sensitivity, a precision of 1% at 800 K is reported for spectral ratio measurements. The technique is demonstrated by 2D measurements of the liquid temperature of burning methanol droplets.