Light‐Induced Conformational Changes in the Plant Cryptochrome Photolyase Homology Region Resolved by Selective Isotope Labeling and Infrared Spectroscopy

Plant cryptochromes are photoreceptors that regulate flowering, circadian rhythm and photomorphogenesis in response to blue and UV‐A light. It has been demonstrated that the oxidized flavin cofactor is photoreduced to the neutral radical state via separate electron and proton transfer. Conformational changes have been found in the C‐terminal extension, but few studies have addressed the changes in secondary structure in the sensory photolyase homology region (PHR). Here, we investigated the PHR of the plant cryptochrome from the green alga Chlamydomonas reinhardtii by light‐induced infrared difference spectroscopy in combination with global ¹³C and ¹⁵N isotope labeling. Assignment of the signals is achieved by establishing a labeling strategy for cryptochromes that preserves the flavin at natural abundance. We demonstrate by UV/vis spectroscopy that the integrity of the sample is maintained and by mass spectrometry that the global labeling was highly efficient. As a result, difference bands are resolved at full intensity that at natural abundance are compensated by the overlap of flavin and protein signals. These bands are assigned to prominent conformational changes in the PHR by blue light illumination. We postulate that not only the partial unfolding of the C‐terminal extension but also changes in the PHR may mediate signaling events.     

Properties of Beurling-type submodules via Agler decompositions

In this paper, we study operator-theoretic properties of the compressed shift operators $S_{z_1}$ and $S_{z_2}$ on complements of submodules of the Hardy space over the bidisk $H^2({\mathbb{D}}^2)$. Specifically, we study Beurling-type submodules – namely submodules of the form $\theta H^2({\mathbb{D}}^2)$ for θ inner – using properties of Agler decompositions of θ to deduce properties of $S_{z_1}$ and $S_{z_2}$ on model spaces $H^2({\mathbb{D}}^2)?\theta H^2({\mathbb{D}}^2)$. Results include characterizations (in terms of θ) of when a commutator $[S_{z_j}^{?},S_{z_j}]$ has rank n and when subspaces associated to Agler decompositions are reducing for $S_{z_1}$ and $S_{z_2}$. We include several open questions.     

Towers and Fibered Products of Model Structures

Given a left Quillen presheaf of localized model structures, we study the homotopy limit model structure on the associated category of sections. We focus specifically on towers and fibered products (pullbacks) of model categories. As applications we consider Postnikov towers of model categories, chromatic towers of spectra and Bousfield arithmetic squares of spectra. For stable model categories, we show that the homotopy fiber of a stable left Bousfield localization is a stable right Bousfield localization.     

Rank one perturbations and singular integral operators

We consider rank one perturbations Aα=A+α(⋅,φ)φ of a self-adjoint operator A with cyclic vector φ∈H−1(A) on a Hilbert space H. The spectral representation of the perturbed operator Aα is given by a singular integral operator of special form. Such operators exhibit what we call ‘rigidity’ and are connected with two weight estimates for the Hilbert transform. Also, some results about two weight estimates of Cauchy (Hilbert) transforms are proved. In particular, it is proved that the regularized Cauchy transforms Tε are uniformly (in ε) bounded operators from L²(μ) to L²(μα), where μ and μα are the spectral measures of A and Aα, respectively. As an application, a sufficient condition for Aα to have a pure absolutely continuous spectrum on a closed interval is given in terms of the density of the spectral measure of A with respect to φ. Some examples, like Jacobi matrices and Schrödinger operators with L² potentials are considered.     

Deviatoric stress driven formation of large single-crystal PbS nanosheet from nanoparticles and in situ monitoring of oriented attachment

Two-dimensional single-crystal PbS nanosheets were synthesized by deviatoric stress-driven orientation and attachment of nanoparticles (NPs). In situ small- and wide-angle synchrotron X-ray scattering measurements on the same spot of the sample under pressure coupled with transmission electron microscopy enable reconstruction of the nucleation route showing how enhanced deviatoric stress causes ordering NPs into single-crystal nanosheets with a lamellar mesostructure. At the same time that deviatoric stress drives SC(110) orientation in a face-centered-cubic supercrystal (SC), rocksalt (RS) NPs rotate and align their RS(200) and RS(220) planes within the SC(110) plane. When NPs approach each other along the compression axis, enhanced deviatoric stress drives soft ligands passivated at RS(200) and RS(220) surfaces to reorient from a group of SC(110) in-planes to the interspace of SC[110]-normal planes. While the internal NP structure starts a rocksalt-to-orthorhombic transition at 7.1 GPa, NPs become aligned on RS(220) and RS(200) and thus become attached at those faces. The transition-catalyzed surface atoms accelerate the inter-NP coalescing process and the formation of low-energy structure nanosheet. Above 11.6 GPa, the nucleated single-crystal nanosheets stack into a lamellar mesostructure that has a domain size comparable to the starting supercrystal.     

Biomimetic silver-containing colloids of poly(2-methacryloyloxyethyl phosphorylcholine) and their film-formation properties

The synthesis of stable dispersions of hybrid colloids comprising copolymers of biocompatible 2-hydroxyethyl methacrylate (HEMA) and zwitterionic, biomimetic 2-methacryloyloxyethyl phosphorylcholine (MPC) incorporating antibacterial AgBF(4) by inverse miniemulsion is described. The prepared hybrid colloids were designed to provide both antibacterial and antifouling properties for the formation of interesting, multifunctional films. The obtained particles had sizes in the range of 130-160 nm with two different weight ratios of MPC to HEMA (1:10 and 2:5) and AgBF(4) contents between 0% and 15%. The silver salt takes on the role of the lipophobe in stabilizing the miniemulsion droplets against Ostwald ripening and is reduced after polymerization to Ag nanoparticles by gaseous hydrazine. Subsequently, the hybrid particles are transformed into smooth and stable films with thicknesses between 145 and 225 nm by simple drop casting and solvent annealing. The dispersions and films were thoroughly characterized by DLS, TEM, SEM, EDX, TGA, UV-vis spectroscopy, ICP-OES, XRD, AFM, and contact angle measurements. After immersion into water, the films did not show detectable leakage of silver, so they could be employed as dual-functional antifouling and antibacterial coatings.     

Benzyl N‐[(Benzyloxy)methyl]carbamate: An Improved Aminomethylation Electrophile for the Synthesis of (Benzyloxy)carbonyl (Cbz)‐Protected Chiral β2‐Amino Acids

α‐Aminomethylation of (R)‐DIOZ‐alkylated (DIOZ=4‐isopropyl‐5,5‐diphenyloxazolidin‐2‐one) substrates is a key step in the asymmetric synthesis of β²‐amino acids, but it is unfortunately often accompanied by formation of transcarbamation by‐products. Aminomethylation was tested using a range of electrophiles, and the amount of by‐product formation was assessed in each case. Benzyl N‐[(benzyloxy)methyl]carbamate electrophile 3d is unable to form this by‐product due to its inherent benzyl substitution. Use of electrophile 3d showed an improved impurity profile in aminomethylation, thus leading to easier intermediate purification.     

Über einige Derivate des Orthochlorbenzaldehyds und der Melilotsäure

Ohne Zusammenfassung