Z(basic)--a novel purification tag for efficient protein recovery

A positively charged protein domain, Z(basic), can be used as a general purification tag to achieve efficient recovery of recombinantly produced target proteins using cation-exchange chromatography. To construct a protein domain usable for ion-exchange chromatography, the surface of protein Z was engineered to be highly charged, which allowed for selective capture of target proteins on a cation-exchanger at physiological pH values. Interestingly, the novel domain, denoted Z(basic), was shown to be selective also under denaturing conditions and could preferably be used for purification of proteins solubilised from inclusion bodies. Moreover, a flexible process for solid-phase refolding was developed, using Z(basic) as a reversible linker to the cation-exchanger resin. This procedure has the inherited advantage of combining purification and refolding into a single step and still enabling elution of a concentrated product in a suitable buffer. This article summarizes development and use of the Z(basic) tag in small and pilot-plant-scale downstream processing.     

The enantioselective synthesis of (-)-lycoramine with the Birch-Cope sequence

The first enantioselective synthesis of (-)-lycoramine has been achieved in 14 steps and 5% overall yield from the biaryl derivative 1. The synthesis applies the previously developed Birch-Cope sequence to create the key arylic quaternary stereocenter of (-)-lycoramine with excellent enantioselective control. The product of the Birch-Cope sequence, a versatile 4,4-disubstituted-2-carboxamide-2-cyclohexen-1-one, was elaborated through an intramolecular conjugate addition of a phenol to create the dihydrofuran ring. Chemoselective elaboration of the allyl group into an amide followed by a modified Pictet-Spengler reaction generated the azepine ring.     

Electron-nuclear dynamics in a quantum dot under nonunitary electron control

We introduce a method for solving the problem of an externally controlled electron spin in a quantum dot interacting with host nuclei via the hyperfine interaction. Our method accounts for generalized (nonunitary) evolution effected by external controls and the environment, such as coherent lasers combined with spontaneous emission. As a concrete example, we develop the microscopic theory of the dynamics of nuclear-induced frequency focusing as first measured in Science 317, 1896 (2007); we find that the nuclear relaxation rates are several orders of magnitude faster than those quoted in that work.     

Synthesis of [(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]azines

The reactions of 2-, 3- and 4-aminopyridines with 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) 4 to give N-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)pyridin-X-amines 1a (X = 2), 1g (X = 3) and 1k (X = 4) were optimized with respect to base, temperature and reaction time. Based on these conditions a total of thirteen [(dithiazolylidene)amino]azines 1a-m were prepared and fully characterized.     

Cation ordering in natural and synthetic (Cu(1-x)Zn(x))(2)CO(3)(OH)(2) and (Cu(1-x)Zn(x))(5)(CO(3))(2)(OH)(6)

In the present paper we report combined experimental and theoretical studies of the UV-vis-NIR spectra of the mineral compounds malachite, rosasite, and aurichalcite and of the precursor compounds for Cu/ZnO catalysts. For the copper species in the minerals the crystal field splitting and the vibronic coupling constants are estimated using the exchange charge model of the crystal field accounting for the exchange and covalence effects. On this basis the transitions responsible for the formation of the optical bands arising from the copper centers in minerals are determined and the profiles of the absorption bands corresponding to these centers are calculated. The profiles of the absorption bands calculated as a sum of bands of their respective Cu species are in quite good agreement with the experimental data. In agreement with crystal chemical considerations, the Zn ions were found to be preferentially located on the more regular, i.e., less distorted, octahedral sites in zincian malachite and rosasite, suggesting a high degree of metal ordering in these phases. This concept also applies for the mineral aurichalcite, but not for synthetic aurichalcite, which seems to exhibit a lower degree of metal ordering. The catalyst precursor was found to be a mixture of zincian malachite and a minor amount of aurichalcite. The best fit of the optical spectrum is obtained assuming a mixture of contributions from malachite (0% Zn) and rosasite (38% Zn of [Zn + Cu]), which is probably due to the intermediate Zn content of the precursor (30%).     

Glycosylated nucleoside lipid promotes the liposome internalization in stem cells

We report new glycosyl-nucleoside-lipid based liposomes decorated with sugar moieties. The GNL-liposomes feature a suitable glycosylated surface for their internalization into ADSC stem cells.     

Simple inexpensive boron electrophiles for direct arene borylation

Electrophilic direct borylation is facilitated, and arene substrate scope enhanced, by using electrophiles derived from inexpensive reagents; specifically an amine, BCl(3) and AlCl(3).     

Formation of the same pyrimido[1,2-a]indoles from 1-(oxiran-2-ylmethyl)-1H-indole or [1,3]oxazolo[3,2-a]indole derivatives in its reactions with aromatic amines

Reactions of two isomers—2-chloro-1-(oxiran-2-ylmethyl)-1H-indole-3-carbaldehyde or 2-(chloromethyl)-2,3-dihydro[1,3]oxazolo[3,2-a]indole-9-carbaldehyde with aromatic amines lead to the same products in both cases—hydrochlorides of pyrimido[1,2-a]indole derivatives containing two fragments of an amine per one part of the indole nucleus. Its structure was confirmed by X-ray analysis of the crystals base, obtained by alkali treatment of the reaction product (when aryl is 4-MeOC₆H₄).     

Filamentary plasma eruptions: Results using the non‐linear ballooning model

This paper provides an overview of recent results on two distinct studies exploiting the non‐linear model for ideal ballooning modes with potential applications to edge‐localized modes (ELMs). The non‐linear model for tokamak geometries was developed by Wilson and Cowley in 2004 and consists of two differential equations that characterize the temporal and spatial evolution of the plasma displacement. The variation of the radial displacement along the magnetic field line is described by the first equation, which is identical to the linear ballooning equation. The second differential equation is a two‐dimensional non‐linear ballooning‐like equation, which is often second order in time but can involve a fractional time derivative depending on the geometry. In the first study, the interaction of multiple filamentary eruptions is addressed in a magnetized plasma in a slab geometry. Equally sized filaments evolve independently in both the linear and non‐linear regimes. However, if filaments are initiated with slightly different heights from the reference flux surface, they interact with each other in the non‐linear regime: lower filaments are slowed down and are eventually completely suppressed, while the higher filaments grow faster because of the non‐linear interaction. In the second study, this model of non‐linear ballooning modes is examined quantitatively against experimental observations of ELMs in Mega Amp Spherical Tokamak (MAST) geometries. The results suggest that experimentally relevant results can only be obtained using modified equilibria.     

Controlled Diels–Alder “Click” Strategy to Access Mechanically Aligned Main-Chain Liquid Crystal Networks

Aligned liquid crystal polymers are materials of interest for electronic, optic, biological and soft robotic applications. The manufacturing and processing of these materials have been widely explored with mechanical alignment establishing itself as a preferred method due to its ease of use and widespread applicability. However, the fundamental chemistry behind the required two-step polymerization for mechanical alignment has limitations in both fabrication and substrate compatibility. In this work we introduce a new protection-deprotection approach utilizing a two-stage Diels–Alder cyclopentadiene-maleimide step-growth polymerization to enable mild yet efficient, fast, controlled, reproducible and user-friendly polymerizations, broadening the scope of liquid crystal systems. Thorough characterization of the films by DSC, DMA, POM and WAXD show the successful synthesis of a uniaxially aligned liquid crystal network with thermomechanical actuation abilities.