Microwave-assisted synthesis of 3-hydroxy-4-pyridinone/naphthalene conjugates. Structural characterization and selection of a fluorescent ion sensor

Two novel 3-hydroxy-4-pyridinone/naphthalene conjugates (L1 and L2) with different distances between the chelating and the fluorescent moieties were synthesized using conventional heating and microwave irradiation achieving a shorter reaction time. The structure of both compounds was confirmed by X-ray crystallography, revealing that these compounds were isolated as hydrochloride salts in dihydroxypyridinium forms. In solution and in the presence of a base, the tautomeric keto forms may be obtained as it was elucidated by NMR analysis. The dihydroxypyridinium form of L1 exhibits fluorescence at 450 nm, both in ACN and DMSO, whereas the corresponding keto form exhibits fluorescence at 365 nm. In contrast, the dihydroxypyridinium form of L2 only fluoresces in DMSO, exhibiting a band at 340 nm, while the keto form is non-fluorescent. These distinct fluorescent behaviors reveal that the tautomeric form in which the ligands are isolated and the distance between the chelating and fluorescent functions strongly influences their fluorescence properties. Ligand L1 exhibits better fluorescence properties and its fluorescence intensity is quenched in the presence of variable concentration of Cu²⁺, Zn²⁺, and Fe³⁺, thus making it suitable to be used as ion sensor.     

Hot or not—the influence of elevated temperature and microwave irradiation on the solid phase synthesis of an affibody

Despite the advances of solid phase peptide synthesis (SPPS) the synthesis of long peptides is still challenging. Microwave irradiation and conventional heating are considered to improve the efficiency of SPPS. It has been shown that conventional heating and heating by microwave irradiation improves the efficiency of solid phase synthesis of peptides that are prone to aggregation as compared to the synthesis at room temperature. In this Letter, the influence of elevated temperature and microwave irradiation on the homogeneity of the synthesis product of a 58-mer peptide affibody has been compared. A detailed analysis by high resolution HPLC and LC-MS mass spectrometry using a high-mass resolution Orbitrap Exactive mass spectrometer was performed. This study revealed that neither thermal heating nor microwave heating improves the yield and purity of the crude product as compared to the synthesis at room temperature. In contrast, the formation of undesirable side products rather increased by microwave irradiation. These results indicate that neither heating nor microwave enhancement of solid phase synthesis does allow a significant improvement of peptide sequences with a low aggregation potential.     

Processive replication of single DNA molecules in a nanopore catalyzed by phi29 DNA polymerase

Coupling nucleic acid processing enzymes to nanoscale pores allows controlled movement of individual DNA or RNA strands that is reported as an ionic current/time series. Hundreds of individual enzyme complexes can be examined in single-file order at high bandwidth and spatial resolution. The bacteriophage phi29 DNA polymerase (phi29 DNAP) is an attractive candidate for this technology, due to its remarkable processivity and high affinity for DNA substrates. Here we show that phi29 DNAP-DNA complexes are stable when captured in an electric field across the α-hemolysin nanopore. DNA substrates were activated for replication at the nanopore orifice by exploiting the 3'-5' exonuclease activity of wild-type phi29 DNAP to excise a 3'-H terminal residue, yielding a primer strand 3'-OH. In the presence of deoxynucleoside triphosphates, DNA synthesis was initiated, allowing real-time detection of numerous sequential nucleotide additions that was limited only by DNA template length. Translocation of phi29 DNAP along DNA substrates was observed in real time at ?ngstrom-scale precision as the template strand was drawn through the nanopore lumen during replication.     

Simultaneous pH and Temperature Measurements Using Pyranine as a Molecular Probe

Steep variations in concentration and temperature frequently occur in small fluid compartments such as those found in cells or microfluidic devices. A quantitative characterization of concentration and temperature gradients is therefore required before these systems can be fully understood. Although different spatially resolved fluorescence methods have been developed to measure either the temperature or the concentration of ions such as proton or calcium, often concentration measurements depend on temperature and vice versa. Here, we describe a method allowing simultaneous measurement of pH and temperature. This method is based on the detection of the blinking of the fluorescent pH indicator pyranine, a process due to its alternating between a basic form and an acidic form. Fluorescence correlation spectroscopy allows measuring both the protonation and deprotonation rates of pyranine, and each pair of rates can be uniquely related to a pair of pH and temperature values. We show, however, that the relationship between rates, pH and temperature, is very sensitive to the presence of other acid-base molecules in solution. We also show that it is influenced by the overall ionic strength of the solution, in a manner that depends on buffer composition.     

Curve following in illiquid markets

In this article the problem of curve following in an illiquid market is addressed. The optimal control is characterised in terms of the solution to a coupled FBSDE involving jumps via the technique of the stochastic maximum principle. Analysing this FBSDE, we further show that there are buy and sell regions. In the case of quadratic penalty functions the FBSDE admits an explicit solution which is determined via the four step scheme. The dependence of the optimal control on the target curve is studied in detail.     

Static observers in curved spaces and non-inertial frames in Minkowski spacetime

Static observers in curved spacetimes may interpret their proper acceleration as the opposite of a local gravitational field (in the Newtonian sense). Based on this interpretation and motivated by the equivalence principle, we are led to investigate congruences of timelike curves in Minkowski spacetime whose acceleration field coincides with the acceleration field of static observers of curved spaces. The congruences give rise to non-inertial frames that are examined. Specifically, we find, based on the locality principle, the embedding of simultaneity hypersurfaces adapted to the non-inertial frame in an explicit form for arbitrary acceleration fields. We also determine, from the Einstein equations, a covariant field equation that regulates the behavior of the proper acceleration of static observers in curved spacetimes. It corresponds to an exact relativistic version of the Newtonian gravitational field equation. In the specific case in which the level surfaces of the norm of the acceleration field of the static observers are maximally symmetric two-dimensional spaces, the energy?Cmomentum tensor of the source is analyzed.     

Realization of reflectionless potentials in photonic lattices

We realize experimentally a true reflectionless potential, which facilitates nonresonant unity transmission for all incident waves and at the same time supports localized modes. We utilize arrays of evanescently coupled optical waveguides, where a particular modulation of the transverse waveguide separations provides a physical realization of reflectionless Ablowitz-Ladik soliton potentials.     

Cosmological classicalization: maintaining unitarity under relevant deformations of the Einstein-Hilbert action

Generic relevant deformations of Einstein's gravity theory contain additional degrees of freedom that have a multifaceted stabilization dynamics on curved spacetimes. We show that these relevant degrees of freedom are self-protected against unitarity violations by the formation of classical field lumps that eventually merge to a new background geometry. The transition is heralded by the massive decay of the original vacuum and evolves through a strong coupling regime. This process fits in the recently proposed classicalization mechanism and extends it further to free field dynamics on curved backgrounds.     

Classical analogue of displaced Fock states and quantum correlations in Glauber-Fock photonic lattices

Coherent states and their generalizations, displaced Fock states, are of fundamental importance to quantum optics. Here we present a direct observation of a classical analogue for the emergence of these states from the eigenstates of the harmonic oscillator. To this end, the light propagation in a Glauber-Fock waveguide lattice serves as equivalent for the displacement of Fock states in phase space. Theoretical calculations and analogue classical experiments show that the square-root distribution of the coupling parameter in such lattices supports a new family of intriguing quantum correlations not encountered in uniform arrays. Because of the broken shift invariance of the lattice, these correlations strongly depend on the transverse position. Consequently, quantum random walks with this extra degree of freedom may be realized in Glauber-Fock lattices.     

Electrical detection of coherent nuclear spin oscillations in phosphorus-doped silicon using pulsed ENDOR

We demonstrate the electrical detection of pulsed X-band electron nuclear double resonance (ENDOR) in phosphorus-doped silicon at 5 K. A pulse sequence analogous to Davies ENDOR in conventional electron spin resonance is used to measure the nuclear spin transition frequencies of the (31)P nuclear spins, where the (31)P electron spins are detected electrically via spin-dependent transitions through Si/SiO(2) interface states, thus not relying on a polarization of the electron spin system. In addition, the electrical detection of coherent nuclear spin oscillations is shown, demonstrating the feasibility to electrically read out the spin states of possible nuclear spin qubits.