Synthesis, structure determination, and (radio-)fluorination of novel functionalized phosphanes suitable for the traceless Staudinger ligation

An elegant and efficient synthesis approach for the preparation of novel benzoate and nicotinate containing phosphanes is presented. This reaction path has a broad substrate scope. Thus, various functionalized phosphanes were obtained in high yields using an esterification procedure under Steglich conditions. A facile blocking of the phosphorus atom with BH₃ was carried out. BH₃ as easily insertable and removable protecting group enables a further derivatization of the benzoate residue. The prepared phosphane derivatives proved to be valuable labeling building blocks for the implementation of a bioorthogonal (radio-)fluorination strategy and were applied for labeling purposes using the traceless Staudinger ligation. For this purpose, a selection of azide-functionalized small organic and bioactive sample molecules was prepared. Furthermore, a mild and selective (radio-)fluorination of these derivatives is demonstrated adopting this bioorthogonal ligation method.     

On deflection fields, weak-focusing and strong-focusing storage rings for polar molecules

In this paper, we analyze electric deflection fields for polar molecules in terms of a multipole expansion and derive a simple but rather insightful expression for the force on the molecules. Ideally, a deflection field exerts a strong, constant force in one direction, while the force in the other directions is zero. We show how, by a proper choice of the expansion coefficients, this ideal can be best approximated. We present a design for a practical electrode geometry based on this analysis. By bending such a deflection field into a circle, a simple storage ring can be created; the direct analog of a weak-focusing cyclotron for charged particles. We show that for realistic parameters a weak-focusing ring is only stable for molecules with a very low velocity. A strong-focusing (alternating-gradient) storage ring can be created by arranging many straight deflection fields in a circle and by alternating the sign of the hexapole term between adjacent deflection fields. The acceptance of this ring is numerically calculated for realistic parameters. Such a storage ring might prove useful in experiments looking for an EDM of elementary particles.     

Chemical, antioxidant and antimicrobial investigations of Pinus cembra L. bark and needles

The chemical constituents and biological activity of Pinus cembra L. (Pinaceae), native to the Central European Alps and the Carpathian Mountains, are not well known. The aim of the present work was to examine the phenolic content, antioxidant and antimicrobial effects of hydromethanolic extracts of Pinus cembra L. bark and needles. Bark extract had higher concentrations of total phenolics (299.3 vs. 78.22 mg gallic acid equivalents/g extract), flavonoids (125.3 vs. 19.84 mg catechin equivalents/g extract) and proanthocyanidins (74.3 vs. 12.7 mg cyanidin equivalents/g extract) than needle extract and was more active as a free radical scavenger, reducing agent and antimicrobial agent. The EC?? values in the 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) and reducing power assays were 71.1, 6.3 and 26 mg/mL for bark extract and 186.1, 24 and 104 mg/mL for needle extract, respectively. In addition, needle extract showed ferrous ions chelating effects (EC?? = 1,755 μg/mL). The antimicrobial effects against Staphylococcus aureus, Sarcina lutea, Bacillus cereus, Escherichia coli, Pseudomonas aeruginosa and Candida albicans were assessed by the agar diffusion method. Both extracts (4 mg/well) were active against all the microorganisms tested; bark extract showed higher inhibition on all strains. These results indicate that Pinus cembra L. bark and needles are good sources of phytochemicals with antioxidant and antimicrobial activities.     

Click strategies for single-molecule protein fluorescence

Single-molecule methods have matured into central tools for studies in biology. Foerster resonance energy transfer (FRET) techniques, in particular, have been widely applied to study biomolecular structure and dynamics. The major bottleneck for a facile and general application of these studies arises from the need to label biological samples site-specifically with suitable fluorescent dyes. In this work, we present an optimized strategy combining click chemistry and the genetic encoding of unnatural amino acids (UAAs) to overcome this limitation for proteins. We performed a systematic study with a variety of clickable UAAs and explored their potential for high-resolution single-molecule FRET (smFRET). We determined all parameters that are essential for successful single-molecule studies, such as accessibility of the probes, expression yield of proteins, and quantitative labeling. Our multiparameter fluorescence analysis allowed us to gain new insights into the effects and photophysical properties of fluorescent dyes linked to various UAAs for smFRET measurements. This led us to determine that, from the extended tool set that we now present, genetically encoding propargyllysine has major advantages for state-of-the-art measurements compared to other UAAs. Using this optimized system, we present a biocompatible one-step dual-labeling strategy of the regulatory protein RanBP3 with full labeling position freedom. Our technique allowed us then to determine that the region encompassing two FxFG repeat sequences adopts a disordered but collapsed state. RanBP3 serves here as a prototypical protein that, due to its multiple cysteines, size, and partially disordered structure, is not readily accessible to any of the typical structure determination techniques such as smFRET, NMR, and X-ray crystallography.     

Conformational changes of strong polycations in the presence of divalent counterions and their influence upon the flocculation efficiency

The interaction between strong polycations, which possess the ammonium quaternary centers attached to an acrylic macromolecular chain derived from poly(N,N-dimethylaminoethyl methacrylate) (polycations Q_x), and divalent counterions was investigated by viscometry and turbidimetry. Conformational changes of polycations were influenced by the polycation charge density, counterion nature (SO₄²⁻ or S₂O₈²⁻) and concentration. The morphology of the polycation layers deposited onto silicon wafers has been studied by tapping mode atomic force microscopy, a strong influence of the polycation and ammonium persulfate concentration on the surface topography being observed. The optimum flocculation concentration of polycation decreased and the flocculation window increased in the presence of S₂O₈²⁻, in the destabilization of kaolin model dispersion. Removal of Congo Red from aqueous solution by the complex system formed between polycations and divalent counterions was also investigated. The behavior of polycations Q_x in separation processes was compared with that of one polycation containing 95 mol% N,N-dimethyl-2-hydroxypropyleneammonium chloride units in the backbone (PCA₅).     

The enhancement of oxygen flux on Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) hollow fibers using silver surface modification

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) hollow fibers were fabricated using a phase inversion/sintering method. As oxygen permeation of BSCF hollow fibers is controlled by the rate surface exchange kinetics, catalytic Ag particles were coated on both inner and outer surfaces using chemical deposition method, as verified by SEM and EDX. The Ag coated BSCF membranes showed up to 100% increase in oxygen permeation at 700 °C, and improvements lower than 10% were measured at 950 °C as compared with unmodified membranes. It was found that Ag catalyst surface loading was non-homogenous and concentrated on the perovskite grain boundaries. As a result, lighter Ag surface loading delivered improved oxygen flux while oxygen flux reached a maximum even though in the presence of excess catalyst loading. The catalytic activity of Ag was beneficial in enhancing surface reaction kinetics up to 850 °C attributed to the spillover effect. Above this temperature, the increase in oxygen permeation rate was marginally diminished due to the reduction of the spillover effect.     

The synthesis of Leishmania major phosphoglycan fragments

The triglycosyl monophosphate 1, heptaglycosyl triphosphates 2 and 3, and octaglycosyl triphosphate 4, which are fragments of the phosphoglycan part of Leishmania major lipo- and proteo-phosphoglycans have been prepared using di- and tri-saccharide H-phosphonates for construction of the phosphodiester bridges.     

Current Efficiency,Corrosion and Structural Changes in SnO2-Sb2O3-CuO Inert Anodes for Aluminium Electrolysis

A systematic study was conducted on current efficiency （CE）, corrosion and structural changes in SnO2-based inert anodes （made of 96wt%SnO2＋2wt%Sb2O3＋2wt%CuO） on a laboratory Hall-Heroult aluminium cell. The influence of operating parameters and electrolyte composition on the CE and corrosion process were evaluated. The CE was found to be more than 90% and catastrophic corrosion took place at low percent of Al2O3, high percent of LiF, low cryolite ratio and high current densities. From all the structural changes that took place in the SnO2-based inert anodes, we assumed that the most important contribution was due to the migration of CuO towards the outer limits of the constituent grains of SnO2 based ceramic. The complex process occurred during the formation of various phases and their sintering ability both directly depended on Cu/Sb molar ratio.     

Stereoselective Synthesis of cis,cis‐Configured Perhydroquinoxaline‐5‐Carbonitrile from Cyclohex‐2‐en‐1‐ol

cis,cis‐Configured perhydroquinoxaline‐5‐carbonitrile 10 was synthesized stereoselectively by ditosylation of trans,cis‐2,3‐dihydroxycyclohexane‐1‐carbonitrile 4 and subsequent reaction with ethylenediamine. The diol precursor 4 was stereoselectively obtained by regioselective opening of the epoxide 3 with KCN in water avoiding hazardous Et₂AlCN.