Structures and Properties of NbOF3 and TaOF3 — with a Remark to the O/F Ordering in the SnF4 Type Structure

Powder samples of NbOF₃ und TaOF₃ were prepared by heating mixtures of NbO₂F and NbF₅ or TaO₂F and TaF₅, respectively, in the corresponding stoichiometric ratio in platinum crucibles under argon atmosphere (180—220 °C). Both oxide fluorides are coulourless with a slight greyish tinge. They are sensitive to moisture and decompose in air at room temperature within hours. Both, NbOF₃ and TaOF₃ crystallize as a variant of the SnF₄ type structure, space group I4/mmm. The structures have been refined from X‐ray powder diffraction data using the Rietveld method (a = 3.9675(1) Å, c = 8.4033(1) Å, R_B = 3.60 %, R_p = 4.58 % for NbOF₃ and a = 3.9448(1) Å, c = 8.4860(1) Å, R_B = 2.07 %, R_p = 2.44 % for TaOF₃). Characteristic building units are sheets of corner sharing MX₆ octahedra which are stacked via van der Waals interactions to a three dimensional framework. The occupancy of the two crystallographic sites for the anions by O and F is discussed on the basis of structure refinements, bond order summations, IR and NMR data and calculations of the Madelung parts of the lattice energy.     

Pr(BO2)3 und PrCl(BO2)2: Zwei meta‐Borate des Praseodyms im Vergleich

Pr(BO₂)₃ and PrCl(BO₂)₂: Two Praseodymium meta‐Borates in Comparison Single‐crystalline PrCl(BO₂)₂ can be obtained by the reaction of praseodymium, Pr₆O₁₁ and PrCl₃ with a small excess of B₂O₃ in evacuated silica tubes after seven days at 850 °C. If NaCl is additionally used as flux, single crystals of Pr(BO₂)₃ dominate the main product. Both praseodymium(III) meta‐borates are air and water stable. The crystals of PrCl(BO₂)₂ emerge as long, thin, pale green needles which tend to severe twinning due to their fibrous habit. The crystal structure (triclinic, P1¯; a = 420.56(4), b = 655.42(7), c = 808.34(8) pm, α = 82.361(8), β = 89.173(9), γ = 71.980(7)°, Z = 2) exhibits zigzag chains {[(B1)o^t_1/1O^e_2/2(B2)O^t_1/1O^e_2/2]²⁻} (≡ {[BO₂]⁻}) of corner‐linked [BO₃]³⁻ triangles with syndiotactic orientation of the terminal oxygen atoms which are running parallel to the [100] direction. The Pr³⁺ cations are surrounded by three Cl⁻ and seven O²⁻ anions with the shape of a tetracapped trigonal prism. The green, transparent crystals of Pr(BO₂)₃ (monoclinic, C2/c; a= 984.98(9), b = 809.57(8), c = 641.02(6) pm, β = 126.783(9)°, Z = 4) appear either lath‐shaped or rather spherical. In the crystal structure the B³⁺ cations reside both in trigonal planar as well as in tetrahedral coordination of oxygen atoms. Both types of borate polyhedra ([BO₃]³⁻ and [BO₄]⁵⁻) are linked via corners to form chains of the composition {[(B2)‐O^t_1/1O^e_2/2(B1)O^e_4/2(B2)O^t_1/1O^e_2/2]³⁻} (≡ {[BO₂]⁻}) which run parallel [101]. The coordination sphere of the Pr³⁺ cations consists of ten oxide anions which build up a bicapped square antiprism.     

On-Line Coupling of Separation Techniques to NMR

The hyphenation of chromatographic separation techniques with NMR spectroscopy is one of the most powerful and time-saving methods for the separation and structural elucidation of unknown compounds and molecular compositions of mixtures. Most of the routinely used NMR flow-cells have detection volumes between 40–180 μL for conventional separations with analytical columns, and the newest designs employ detection volumes in the order of 200 nL for capillary separations. The low flow rates used in capillary chromatography permit the use of deuterated solvents. Unequivocal structural assignment of unknown chromatographic peaks is possible by two-dimensional stopped-flow capillary HPLC-NMR experiments.     

Transitions between secondary structures in isolated polyalanines

Monte Carlo simulations of gas-phase polyalanine peptides have been carried out with the Amber ff96 force field. A low-temperature structural transition takes place between the α-helix stable conformation and β-sheet structures, followed by the unfolding phase change. The transition state ensembles connecting the helix and sheet conformations are investigated by sampling the energy landscape along specific geometric order parameters as putative reaction coordinates, namely the electric dipole μ, the end-to-end distance d, and the gyration radius R_g. By performing series of shooting trajectories, the committor probabilities and their distributions are obtained, revealing that only the electric dipole provides a satisfactory transition coordinate for the α↔β interconversion. The nucleus at the transition is found to have a high helical content.     

Interface morphologies and magnetization characteristics of Co70Fe30 thin films deposited on conjugated polymer thin films

The surface and interface morphology and magnetization characteristics of Co₇₀Fe₃₀ thin films deposited on bare glass and p-Si/SiO₂ substrates and on conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) thin films on such substrates have been studied by atomic force microscopy and magneto-optic Kerr effect. It was found that the average absolute magnitude of the coercive field of Co₇₀Fe₃₀ correlates with the roughness of the underlayer prior to Co₇₀Fe₃₀ deposition. P3HT deposited on p-Si/SiO₂ substrates possesses an increased surface roughness as compared to the p-Si/SiO₂ surface, but displays a decreased surface roughness as compared to the one of a bare glass substrate.     

Equilibrium and <Superscript>1</Superscript>H NMR Kinetic Study of the Reactions of Dichlorido [S-Methyl-L-Cysteine(N,S)]Platinum(II) Complex with Some Relevant Biomolecules

The formation equilibria of the [Pt(SMC)(H₂O)₂]⁺ complex with some biologically relevant ligands such as L-methionine (L-met) and glutathione (GSH) were studied. The stoichiometry and stability constants of the formed complexes are reported, and the concentration distribution of the various complex species has been evaluated as a function of pH. The reaction between [PtCl₂(SMC)] and guanosine-5′-monophosphate (5′-GMP) was studied by ¹H NMR spectroscopy. The NMR spectra indicated that first step is the hydrolysis of the [PtCl₂(SMC)] complex and second step is the substitution of an aqua ligand, either in the cis or trans position with guanosine-5′-monophosphate in molar ratio 1:1. The values of rate constant showed faster substitution of coordinated H₂O in the trans position to the S donor atom of S-methyl-L-cysteine, whereas the slower reaction was assigned to the displacement of the cis coordinated aqua molecule. This is due to the strong trans labilization effect of coordinated sulfur. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

New natural products in the discorhabdin A- and B-series from New Zealand-sourced Latrunculia spp. sponges

A survey of the secondary metabolite chemistry profiles of New Zealand sponges of the genus Latrunculia has yielded new members of the discorhabdin A- and B-type families. The structure elucidation of (+)-(6R,8S)-1-thiomethyldiscorhabdin G^∗/I (5) and both enantiomers of 16a,17a-dehydrodiscorhabdin W (6) are reported. Absolute configurations were assigned by comparison with a dataset of recently reported electronic circular dichroism spectra of discorhabdin alkaloids. A stereochemical correction of the recently reported natural product (+)-3-dihydrodiscorhabdin A from (3S,5R,6S,8S)-(7) to the C3-epimeric (+)-(3R,5R,6S,8S)-(8) and assignment of absolute configuration is also presented. Semi-synthesis of (+)-(3S,5R,6S,8S)-(7) from (+)-discorhabdin A provided further evidence for this structure revision. Cytotoxicity data is reported for 5-8.     

Ancistrocladinium A and B, the first N,C-coupled naphthyldihydroisoquinoline alkaloids, from a Congolese ancistrocladus species

The isolation and structural elucidation of three novel-type naphthylisoquinoline alkaloids, ancistrocladinium A and B (the latter along with its atropisomer), from a Congolese Ancistrocladus species collected in the habitat Yeteto is reported. Their structures, including all stereochemical features, were elucidated by spectroscopic, chemical, and chiroptical methods. Ancistrocladinium A and B are the first N,C-coupled naphthyldihydroisoquinoline alkaloids found in nature, i.e., with an iminium-aryl axis. Although ancistrocladinium A, which is N,8'-coupled, is configurationally stable at this axis, ancistrocladinum B and its rotational isomer are based on a hitherto unprecedented N,6'-coupling type, with a slow rotation about the hetero biaryl axis at room temperature; they thus occur as a 46:54 mixture of two configurationally semistable atropo-diastereomers. For the isomerization of (P)-ancistrocladinium B to its (M)-diastereomer and for the opposite direction, the Gibbs free energies of activation were determined to be DeltaG double dagger1 = 105.8 kJ mol-1 and DeltaG double dagger2 = 105.7 kJ mol-1, respectively. In addition, the compounds were shown to have promising antileishmanial activities.     

Mid-infrared supercontinuum generation to 4.5 microm in ZBLAN fluoride fibers by nanosecond diode pumping

A mid-infrared supercontinuum (SC) is generated in ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF...) fluoride fibers from amplified nanosecond laser diode pulses with a continuous spectrum from approximately 0.8 microm to beyond 4.5 microm. The SC has an average power of approximately 23 mW, a pump-to-SC power conversion efficiency exceeding 50%, and a spectral power density of approximately -20 dBm/nm over a large fraction of the spectrum. The SC generation is initiated by the breakup of nanosecond laser diode pulses into femtosecond pulses through modulation instability, and the spectrum is then broadened primarily through fiber nonlinearities in approximately 2-7 m lengths of ZBLAN fiber. The SC long-wavelength edge is consistent with the intrinsic ZBLAN material absorption.     

Diamond Quantum Devices in Biology

The currently available techniques for molecular imaging capable of reaching atomic resolution are limited to low temperatures, vacuum conditions, or large amounts of sample. Quantum sensors based on the spin‐dependent photoluminescence of nitrogen‐vacancy (NV) centers in diamond offer great potential to achieve single‐molecule detection with atomic resolution under ambient conditions. Diamond nanoparticles could also be prepared with implanted NV centers, thereby generating unique nanosensors that are able to traffic into living biological systems. Therefore, this technique might provide unprecedented access and insight into the structure and function of individual biomolecules under physiological conditions as well as observation of biological processes down to the quantum level with atomic resolution. The theory of diamond quantum sensors and the current developments from their preparation to sensing techniques have been critically discussed in this Minireview.