One‐Dimensional Arsenic Allotropes: Polymerization of Yellow Arsenic Inside Single‐Wall Carbon Nanotubes

The pnictogen nanomaterials, including phosphorene and arsenene, display remarkable electronic and chemical properties. Yet, the structural diversity of these main group elements is still poorly explored. Here we fill single‐wall carbon nanotubes with elemental arsenic from the vapor phase. Using electron microscopy, we find chains of highly reactive As₄ molecules as well as two new one‐dimensional allotropes of arsenic: a single‐stranded zig‐zag chain and a double‐stranded zig‐zag ladder. These linear structures are important intermediates between the gas‐phase clusters of arsenic and the extended sheets of arsenene. Raman spectroscopy indicates weak electronic interaction between the arsenic and the nanotubes which implies that the formation of the new allotropes is driven primarily by the geometry of the confinement. The relative stabilities of the new arsenic structures are estimated computationally. Band‐gap calculations predict that the insulating As₄ chains become semiconducting, once converted to the zig‐zag ladder, and form a fully metallic allotrope of arsenic as the zig‐zag chain.     

Enantio‐ and Diastereoselective Synthesis of Chiral Allenes by Palladium‐Catalyzed Asymmetric [3+2] Cycloaddition Reactions

A protocol for the asymmetric synthesis of highly substituted chiral allenes with control of point and axial chirality has been developed. A palladium‐catalyzed [3+2] cycloaddition using readily available racemic allenes gives access to densely functionalized chiral allenes with excellent yields and functional group tolerance. The catalytic asymmetric protocol utilizes a broad range of allenyl TMM (trimethylenemethane) donors to form cyclopentanes, pyrrolidines, and spirocycles with very good control of regio‐, enantio‐, and diastereoselectivity. The chiral allene moiety is shown to be a valuable functional group for rapid elaboration towards complex targets.     

Kinetic Resolution of sec‐Thiols by Enantioselective Oxidation with Rationally Engineered 5‐(Hydroxymethyl)furfural Oxidase

Various flavoprotein oxidases were recently shown to oxidize primary thiols. Herein, this reactivity is extended to sec‐thiols by using structure‐guided engineering of 5‐(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of racemic sec‐thiols, thus yielding the corresponding thioketones and nonreacted R‐configured thiols with excellent enantioselectivities (E≥200). The engineering strategy applied went beyond the classic approach of replacing bulky amino acid residues with smaller ones, as the active site was additionally enlarged by a newly introduced Thr residue. This residue established a hydrogen‐bonding interaction with the substrates, as verified in the crystal structure of the variant. These strategies unlocked HMFO variants for the enantioselective oxidation of a range of sec‐thiols.     

The beam propagation method: An analysis of its applicability

Corrigenda

The beam propagation method: An analysis of its applicability     

Liquid chromatographic-mass spectrometric separation of oligoalanine peptide stereoisomers: influence of absolute configuration on enantioselectivity and two-dimensional separation of diastereomers and enantiomers

This contribution describes the chromatographic separation of peptide stereoisomers. Thereby, one focus is laid on the influence of the absolute configurations of peptide enantiomer pairs on their enantioselective separation. Three different N-terminal protecting groups and three different chiral stationary phases (CSPs) based on cinchona alkaloid derivatives were employed and oligoalanine di-, tri- and tetra-peptides were used as model set. The absolute configurations of the individual enantiomeric pairs were found to profoundly influence both the elution order and the enantioselectivity. The stereoselective molecular recognition mechanism was observed to be dependent on the combination of configuration and the chosen protecting group and CSP. As the CSPs on their own exhibited insufficient diastereoselectivity, a two-dimensional liquid chromatography-mass spectrometry (LC-MS) system was developed for the separation of both diastereomers and enantiomers of peptides in the second part of this study. Diastereomers were separated by reversed phase (RP) and the resulting enantiomeric pair fractions were transferred to a CSP for enantioseparation. All eight stereoisomers of a tripeptide (Ala-Ala-Ala) and 9 out of 10 stereoisomers of a tetrapeptide (Ala-Ala-Ala-Ala) could be successfully resolved.     

The first stable beta-fluorosilylanion

The reaction of 2 equiv of tris(trimethylsilyl)silylfluoride with potassium tert-butoxide in the presence of donor molecules (THF, DME, 18-crown-6) leads to the clean formation of an adduct of 1-potassio-2-fluorotetrakis(trimethylsilyl)disilane. Attempts to transmetalate this compound effect the elimination of metal fluoride accompanied by the formation of tetrakis(trimethylsilyl)disilene. The latter can either be trapped in a cycloaddition reaction or in the absence of trapping reagents dimerizes to octakis(trimethylsilyl)cyclotetrasilane.     

Pluronic microemulsions as nanoreservoirs for extraction of bupivacaine from normal saline

We hypothesized that custom-designed microemulsions would effectively scavenge compounds from bulk media. Pluronic-based oil-in-water microemulsions were synthesized that efficiently reduced the free concentration of the local anesthetic bupivacaine in 0.9% NaCl. Both the molecular nature and concentration of the constituents in the microemulsions significantly affected extraction efficiencies. Pluronic F127-based microemulsions extracted bupivacaine more efficiently than microemulsions synthesized using other Pluronic surfactants (L44, L62, L64, F77, F87, F88, P104). Extraction was markedly increased by addition of fatty acid sodium salts due to greater oil/water interface area, increased columbic interaction between bupivacaine and fatty acids sodium salt, and greater surface activity. These data suggest that oil-in-water microemulsions may be an effective agent to treat cardiotoxicity caused by bupivacaine or other lipophilic drugs.     

Downregulation of COP9 signalosome subunits differentially affects the CSN complex and target protein stability

Background  

The COP9 signalosome (CSN) is a conserved protein complex in eukaryotic cells consisting of eight subunits (CSN1 to CSN8). Recent data demonstrate that the CSN is a regulator of the ubiquitin (Ub) proteasome system (UPS). It controls substrate ubiquitination by cullin-RING Ub ligases (CRLs), a process that determines substrate specificity of the UPS. The intrinsic deneddylating activity localized to CSN5 as well as the associated kinases and deubiquitinating activity are involved in the regulatory function of CSN. The exact mechanisms are unclear. In this study we knocked down CSN1 (siCSN1), CSN3 (siCSN3) and CSN5 (siCSN5) by specific siRNA oligos permanently expressed in HeLa cells. The analysis and comparison of siRNA cells revealed differential impact of individual subunits on CSN structure and function.     

X-ray structures,photophysical characterization,and computational analysis of geometrically constrained copper(I)--phenanthroline complexes

A series of three geometrically constrained C(2)-symmetric Cu(I) mono-phenanthroline complexes were characterized by X-ray structural analysis, and their photophysical properties were investigated by absorption and emission spectroscopy. Visible light excitation yielded metal-to-ligand charge-transfer (MLCT) excited states with luminescence lifetimes up to 155 ns. Ultrafast transient absorption spectroscopy provided further insights into the excited-state dynamics and suggests for all three complexes the formation of a phenanthroline radical anion. In agreement with electrochemical measurements, the data further indicate that coordinative rearrangements are involved in nonradiative deactivation of the excited states. According to time-dependent density functional theory calculations (B3LYP/6-31G), the major MLCT transitions are polarized along the C(2) axis of the complex and originate predominantly from the copper d(xz) orbital. The computational analysis identifies an excited-state manifold with a number of close-lying, potentially emissive triplet states and is in agreement with the multiexponential decay kinetics of the MLCT luminescence. The relationship between structural and photophysical data of the studied Cu(I) mono-phenanthroline complexes agrees well with current models describing the photophysics of the related Cu(I) bis-diimine complexes.     

Crystal structure of (S,S)-diphenylethanediammonium (R,R)-tartrate

Summary The crystal structure of (–)-diphenylethanediammonium-(R,R)-tartrate was determined. From this structure determination, the (S,S) configuration was assigned to the (–)-diphenylethanediamine. The asymmetric unit of the crystal structure contains two units of the title compound plus one molecule of ethanol and one water molecule, which form an intricate network of 19 hydrogen bonds.

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Die Kristallstruktur von (S,S)-Diphenylethandiammonium-(R,R)-tartrat

Zusammenfassung Es wurde die Kristallstruktur von (–)-Diphenylethandiammonium-(R,R)-tartrat bestimmt. Aus dieser Strukturbestimmung ergab sich die Zuordnung der (S,S)-Konfiguration zum (–)-Diphenylethandiamin. Die asymmetrische Einheit der Kristallstruktur besteht aus zwei Formeleinheiten der Titelverbindung sowie einem Molekül Ethanol und einem Wassermolekül, welche ein komplexes Netzwerk von insgesamt 19 Wasserstoffbrücken bilden.