New stannide ScAgSn: determination of the superstructure via two-dimensional 45Sc solid state NMR

The new stannide ScAgSn was synthesized by induction melting of the elements in a sealed tantalum tube and subsequent annealing. ScAgSn crystallizes with a pronounced subcell structure: ZrNiAl type, P2m, a = 708.2(2) pm, c = 433.9(1) pm, wR2 = 0.1264, 321 F2 values, and 14 variables. The Guinier powder pattern reveals weak superstructure reflections pointing to a TiFeSi-type structural arrangement: I2cm, a = 708.1(1) pm, b = 1225.2(2) pm, c = 869.9(1) pm, wR2 = 0.0787, 5556 F2 values, and 49 variables. So far the growth of high-quality single crystals failed. Determination of the superstructure was partly based on merohedral triplet X-ray data augmented by 119Sn M?ssbauer spectroscopy and 119Sn and 45Sc solid-state NMR data. In particular, the observation of three crystallographically inequivalent sites in 45Sc NMR triple quantum magic-angle spinning (TQ-MAS) NMR spectra provided unambiguous proof of the superstructure proposed. The ScAgSn structure consists of a three-dimensional [AgSn] network (with Ag-Sn distances between 273 and 280 pm) in which the scandium atoms are located in distorted hexagonal channels, each having five tin and two silver nearest neighbors. Both crystallographically independent tin sites have a tricapped trigonal prismatic coordination, that is, [Sn1Sc6Ag3] and [Sn2Ag6Sc3] environments, which are well distinguished in the 119Sn NMR and M?ssbauer spectra because of their different site symmetries.     

Discotic liquid crystals: from tailor-made synthesis to plastic electronics

Most associate liquid crystals with their everyday use in laptop computers, mobile phones, digital cameras, and other electronic devices. However, in contrast to their rodlike (calamitic) counterparts, first described in 1907 by Vorl?nder, disklike (discotic, columnar) liquid crystals, which were discovered in 1977 by Chandrasekhar et al., offer further applications as a result of their orientation in the columnar mesophase, making them ideal candidates for molecular wires in various optical and electronic devices such as photocopiers, laser printers, photovoltaic cells, light-emitting diodes, field-effect transistors, and holographic data storage. Beginning with an overview of the various mesophases and characterization methods, this Review will focus on the major classes of columnar mesogens rather than presenting a library of columnar liquid crystals. Emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties. Finally, some applications and perspectives in materials science and molecular electronics will be discussed.     

A General Strategy for Targeting Drugs to Bone

Targeting drugs to their desired site of action can increase their safety and efficacy. Bisphosphonates are prototypical examples of drugs targeted to bone. However, bisphosphonate bone affinity is often considered too strong and cannot be significantly modulated without losing activity on the enzymatic target, farnesyl pyrophosphate synthase (FPPS). Furthermore, bisphosphonate bone affinity comes at the expense of very low and variable oral bioavailability. FPPS inhibitors were developed with a monophosphonate as a bone‐affinity tag that confers moderate affinity to bone, which can furthermore be tuned to the desired level, and the relationship between structure and bone affinity was evaluated by using an NMR‐based bone‐binding assay. The concept of targeting drugs to bone with moderate affinity, while retaining oral bioavailability, has broad application to a variety of other bone‐targeted drugs.     

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.     

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.     

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.     

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.