Synthesis and characterization of ratiometric nanosensors for pH quantification: a mixed micelle approach

Optical nanoparticle pH sensors designed for ratiometric measurements have previously been synthesized using post-functionalization approaches to introduce sensor molecules and to modify nanoparticle surface chemistry. This strategy often results in low control of the nanoparticle surface chemistry and is prone to batch-to-batch variations, which is undesirable for succeeding sensor calibrations and cellular measurements. Here we provide a new synthetic approach for preparing nanoparticle pH sensors based on self-organization principles, which in comparison to earlier strategies offers a much higher design flexibility and high control of particle size, morphology and surface chemistry.     

Direct measurement of the formation length of photons

We report the first observation of a shoulder in the radiation spectrum from GeV electrons in a structured target consisting of two thin and closely spaced foils. The position of the shoulder depends on the target spacing and is directly connected to the finite formation length of a low-energy photon emitted by an ultrarelativistic electron. With the present setup it is possible to control the separation of the foils on a μm scale and hence measure interference effects caused by the macroscopic dimensions of the formation length. Several theoretical groups have predicted this effect using different methods. Our observations have a preference for the modified theory by Blankenbecler but disagree with the results of Baier and Katkov.     

On the Stability of Solitary Water Waves with a Point Vortex

This paper investigates the stability of traveling wave solutions to the free boundary Euler equations with a submerged point vortex. We prove that sufficiently small-amplitude waves with small enough vortex strength are conditionally orbitally stable. In the process of obtaining this result, we develop a quite general stability/instability theory for bound state solutions of a large class of infinite-dimensional Hamiltonian systems in the presence of symmetry. This is in the spirit of the seminal work of Grillakis, Shatah, and Strauss (GSS) , but with hypotheses that are relaxed in a number of ways necessary for the point vortex system, and for other hydrodynamical applications more broadly. In particular, we are able to allow the Poisson map to have merely dense range, as opposed to being surjective, and to be state-dependent. As a second application of the general theory, we consider a family of nonlinear dispersive PDEs that includes the generalized Korteweg–de Vries (KdV) and Benjamin-Ono equations. The stability or instability of solitary waves for these systems has been studied extensively, notably by Bona, Souganidis, and Strauss , who used a modification of the GSS method. We provide a new, more direct proof of these results, as a straightforward consequence of our abstract theory. At the same time, we allow fractional dispersion and obtain a new instability result for fractional KdV. © 2020 Wiley Periodicals, Inc.     

Anisotropy enhanced X‐ray scattering from solvated transition metal complexes

Time‐resolved X‐ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X‐ray free‐electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X‐ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time‐resolved X‐ray scattering experiment. This method is applied on time‐resolved X‐ray scattering patterns measured upon photoexcitation of a solvated di‐platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute, i.e. the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.     

Tracing the Photoaddition of Pharmaceutical Psoralens to DNA

The psoralens 8-methoxypsoralen (8-MOP), 4,5′,8-trimethylpsoralen (TMP) and 5-methoxypsoralen (5-MOP) find clinical application in PUVA (psoralen + UVA) therapy. PUVA treats skin diseases like psoriasis and atopic eczema. Psoralens target the DNA of cells. Upon photo-excitation psoralens bind to the DNA base thymine. This photo-binding was studied using steady-state UV/Vis and IR spectroscopy as well as nanosecond transient UV/Vis absorption. The experiments show that the photo-addition of 8-MOP and TMP involve the psoralen triplet state and a biradical intermediate. 5-MOP forms a structurally different photo-product. Its formation could not be traced by the present spectroscopic technique.     

A new chiral, poly-imidazole N8-ligand and the related di- and tri-copper(II) complexes: synthesis, theoretical modelling, spectroscopic properties, and biomimetic stereoselective oxidations

The new poly-imidazole N(8) ligand (S)-2-piperazinemethanamine-1,4-bis[2-((N-(1-acetoxy-3-(1-methyl-1H-imidazol-4-yl))-2-(S)-propyl)-(N-(1-methyl-1H-imidazol-2-ylmethyl)))ethyl]-N-(phenylmethyl)-N-(acetoxy), also named (S)-Pz-(C2-(HisIm))(2) (L), containing three chiral (S) centers, was obtained by a multi-step synthesis and used to prepare dinuclear [Cu(2)(L)](4+) and trinuclear [Cu(3)(L)](6+) copper(II) complexes. Low-temperature EPR experiments performed on [Cu(2)(L)](4+) demonstrated that the two S = ? centers behaved as independent paramagnetic units, while the EPR spectra used to study the trinuclear copper complex, [Cu(3)(L)](6+), were consistent with a weakly coupled three-spin ? system. Theoretical models for the two complexes were obtained by DFT/RI-BP86/TZVP geometry optimization, where the structural and electronic characteristics nicely supported the EPR experimental findings. In addition, the theoretical analysis unveiled that the conformational flexibility encoded in both [Cu(2)(L)](4+) and [Cu(3)(L)](6+) arises not only from the presence of several σ-bonds and the bulky residues attached to the (S)-Pz-(C2-(HisIm))(2) ligand scaffold, but also from the poor coordination ability of the tertiary amino groups located in the ligand side-chains containing the imidazole units towards the copper(II) ions. Both the dinuclear and trinuclear complexes are efficient catalysts in the stereoselective oxidation of several catechols and flavonoid compounds, yielding the corresponding quinones. The structural features of the substrate-catalyst adduct intermediates were assessed by searching the conformational space of the molecule through MMFF94/Monte Carlo (MMFF94/MC) methods. The conformational flexibility of the bound ligand in the complexes proves to be beneficial for substrate binding and recognition. For the dinuclear complex, chiral recognition of the optically active substrates derives from weak electrostatic interactions between bound substrates and folded regions of the ligand scaffold. For the trinuclear complex, in the case of L/D-Dopa, the chiral recognition has a remarkable stereoselectivity index of 75%, the highest so far reported for this type of reaction. Here the dominant contribution to stereoselectivity arises from the direct interaction between a donor group (the Dopa carboxylate) far from the substrate reaction site (the catechol ring) with the additional (third) copper center not involved in the oxidative catalysis. On the other hand, in the case of bulky substrates, such as L/D-catechin, the observed poor substrate recognition is associated with much weaker interactions between the chiral regions of the complex and the chiral part of the substrate.     

Expanding the dynamic measurement range for polymeric nanoparticle pH sensors

Conventional optical nanoparticle pH sensors that are designed for ratiometric measurements in cells have been based on utilizing one sensor fluorophore and one reference fluorophore in each nanoparticle, which results in a relatively narrow dynamic measurement range. This results in substantial challenges when conducting live cell measurements, which often leads to misleading results. In the present work we provide a simple solution to this problem.     

What’s so Good about a Wise and Knowledgeable Public?

Philosophers have been concerned for some time with the epistemic caliber of the general public, qua the body that is, ultimately, tasked with political decision-making in democratic societies. Unfortunately, the empirical data paint a pretty dismal picture here, indicating that the public tends to be largely ignorant on the issues relevant to governance. To make matters worse, empirical research on how ignorance tends to breed overconfidence suggests that the public will not only lack knowledge on the relevant issues, but also wisdom, in the Socratic sense of an awareness of your ignorance. While increasing the knowledge and wisdom of the public might be thought an obvious remedy, there is, as far as sound political decision-making and action are concerned, nothing particularly valuable about knowledge or wisdom per se. In fact, it might just be that what the public needs is nothing but the most basic epistemic good: true belief.     

Goal‐oriented error estimation for Cahn–Hilliard models of binary phase transition

A posteriori estimates of errors in quantities of interest are developed for the nonlinear system of evolution equations embodied in the Cahn–Hilliard model of binary phase transition. These involve the analysis of wellposedness of dual backward‐in‐time problems and the calculation of residuals. Mixed finite element approximations are developed and used to deliver numerical solutions of representative problems in one‐ and two‐dimensional domains. Estimated errors are shown to be quite accurate in these numerical examples. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2010