AFM studies of solid-supported lipid bilayers formed at a Au(111) electrode surface using vesicle fusion and a combination of Langmuir-Blodgett and Langmuir-Schaefer techniques

Atomic force microscopy (AFM) has been used to characterize the formation of a phospholipid bilayer composed of 1,2-dimyristyl-sn-glycero-3-phosphocholine (DMPC) at a Au(111) electrode surface. The bilayer was formed by one of two methods: fusion of lamellar vesicles or by the combination of Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) deposition. Results indicate that phospholipid vesicles rapidly adsorb and fuse to form a film at the electrode surface. The resulting film undergoes a very slow structural transformation until a characteristic corrugated phase is formed. Force-distance curve measurements reveal that the thickness of the corrugated phase is consistent with the thickness of a bilayer lipid membrane. The formation of the corrugated phase may be explained by considering the elastic properties of the film and taking into account spontaneous curvature induced by the asymmetric environment of the bilayer, in which one side faces the gold substrate and the other side faces the solution. The effect of temperature and electrode potential on the stability of the corrugated phase has also been described.     

Affine Processes on Symmetric Cones

We consider affine Markov processes taking values in convex cones. In particular, we characterize all affine processes taking values in irreducible symmetric cones in terms of certain Lévy–Khintchine triplets. This is the natural, coordinate-free formulation of the theory of Wishart processes on positive semidefinite matrices, as put forward by Bru (J Theor Probab 4(4):725–751, 1991) and Cuchiero et al. (Ann Appl Probab 21(2):397–463, 2011), in the more general context of symmetric cones, which also allows for simpler, alternative proofs.     

Separation behavior of electron-beam curing derived, acrylate-based monoliths

Electron beam (EB) curing-derived monolith materials were prepared from ethyl methacrylate (EMA), trimethylolpropane triacrylate (TMPTA), 2-propanol, 1-dodecanol, and toluene within the confines of 3 mmx100 mm id glass columns, applying a total dose of 22 kGy for curing. Monolithic columns were checked for their separation behavior for selected dansylated (DNS)-amino acids as well as for cyclophilin 18. Their separation performance was compared to that of a C18-modified silica-based rigid rod (Chromoliths). In the separation of dansylated amino acids, retention times were reduced on EB-derived columns, where the peak resolution was significantly better than on a Chromolith. This finding was attributed to a larger fraction of small pores (<2.15 nm) in the EB curing-derived monoliths. Finally, EB curing-derived monoliths have been used to separate cyclophilin 18 from crude cell lysis mixtures.     

The Asymmetric Synthesis of the [D8]‐Labeled (−)‐(S)‐Dihydroxyverbacine,the Terminal Precursor in the Biogenesis of the Macrobicyclic Spermine Alkaloids Aphelandrine and Orantine

The asymmetric synthesis of the unlabeled and [D₈]‐labeled terminal precursors, 4 ((−)‐(S)‐dihydroxyverbacine) and 19 , respectively, in the biogenesis of the spermine alkaloids aphelandrine ( 5 ) and orantine ( 6 ), respectively, is described. A partial synthesis of the alkaloid (−)‐(S)‐[(E)‐4‐methoxycinnamoyl]buchnerine ( 10 ) is also presented.     

On-Line Coupling of High-Performance Liquid Chromatography to Atmospheric Pressure Chemical Ionization Mass Spectrometry (HPLC/APCI-MS and MS/MS). The Pollen Analysis of Hippeastrum x hortorum (Amaryllidaceae)

A H₂O/MeOH extract of the pollen of Hippeastrum x hortorum (Amaryllidaceae) was analyzed. A mixture of different compounds (at the most 84) was found, namely the geometrically ((E,E), (E,Z), (Z,E), and (Z,Z) and structurally isomeric N,N′-dicoumaroyl (=N,N′-bis[3-(4-hydroxyphenyl)prop-2-enoyl]), N,N′-diferuloyl (=N,N′-bis[3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl]), N,N′-disinapoyl (=N,N′-bis[3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-enoyl]), N-coumaroyl-N′-feruloyl, and N-feruloyl-N′-sinapoyl derivatives of spermidine (=4-azaoctane-1,8-diamine=N-(3-aminopropyl)butane-1,4-diamine). Their structures were proven by using on-line-coupled high-performance liquid chromatography and atmospheric-pressure chemical-ionization mass spectrometry (HPLC-UV(DAD)/APCI-MS and MS/MS), UV-induced (E)⇌(Z) photoisomerization, and catalytic hydrogenation, as well by comparing their spectra and chromatographic behavior with those of synthetic standards. According to the physicochemical properties of these natural compounds, a proposed biological function is discussed.     

Synthesis of 2,6-disubstituted dihydropyrans via an efficient BiBr3-initiated three component, one-pot cascade

The rapid synthesis of cis-2,6-disubstituted dihydropyrans is achieved in a three-component, one-pot cascade reaction. BiBr₃-mediated addition of ketene silyl acetals or silyl enol ethers to β,γ-unsaturated cis-4-trimethylsilyl-3-butenal provides a Mukaiyama aldol adduct containing a vinylsilane moiety tethered to a silyl ether. Addition of a second aldehyde initiates a domino sequence involving intermolecular addition followed by an intramolecular silyl-modified Sakurai (ISMS) reaction. Isolated yields of this one-pot reaction vary from 44 to 80% and all compounds were isolated as the cis-diastereomers (10 examples).     

Synthesis of BODIPY Derivatives Substituted with Various Bioconjugatable Linker Groups: A Construction Kit for Fluorescent Labeling of Receptor Ligands

The goal of the present study was to design small, functionalized green-emitting BODIPY dyes, which can readily be coupled to target molecules such as receptor ligands, or even be integrated into their pharmacophores. A simple two-step one-pot procedure starting from 2,4-dimethylpyrrole and ω-bromoalkylcarboxylic acid chlorides was used to obtain new ω-bromoalkyl-substituted BODIPY fluorophores (1a–1f) connected via alkyl spacers of different length to the 8-position of the fluorescent dye. The addition of radical inhibitors reduced the amount of side products. The ω-bromoalkyl-substituted BODIPYs were further converted to introduce various functional groups: iodo-substituted dyes were obtained by Finkelstein reaction in excellent yields; microwave-assisted reaction with methanolic ammonia led to fast and clean conversion to the amino-substituted dyes; a hydroxyl-substituted derivative was prepared by reaction with sodium ethylate, and thiol-substituted BODIPYs were obtained by reaction of 1a–1f with potassium thioacetate followed by alkaline cleavage of the thioesters. Water-soluble derivatives were prepared by introducing sulfonate groups into the 2- and 6-position of the BODIPY core. The synthesized BODIPY derivatives showed high fluorescent yields and appeared to be stable under basic, reducing and oxidative conditions. As a proof of concept, 2-thioadenosine was alkylated with bromoethyl-BODIPY 1b. The resulting fluorescent 2-substituted adenosine derivative 15 displayed selectivity for the A₃ adenosine receptor (ARs) over the other AR subtypes, showed agonistic activity, and may thus become a useful tool for studying A₃ARs, or a lead structure for further optimization. The new functionalized dyes may be widely used for fluorescent labeling allowing the investigation of biological targets and processes.     

Formation of HO2 radicals from the 248 nm two-photon excitation of different aromatic hydrocarbons in the presence of O2

The excitation energy dependence of HO(2) radical formation from the 248 nm irradiation of four different aromatic hydrocarbons (benzene, toluene, o-xylene, and mesitylene) in the presence of O(2) has been studied. HO(2) has been monitored at 6638.20 cm(-1) by cw-CRDS, and the formation of a short-lived, unidentified species, showing broad-band absorption around the HO(2) absorption line, has been observed. For all four hydrocarbons, the same HO(2) formation pattern has been observed: HO(2) is formed immediately on our time scale after the excitation pulse, followed by a formation of more HO(2) on a much longer time scale. Taking into account the absorption of the short-lived species, the yields of both types of HO(2) radicals are in agreement with a formation following 2-photon absorption by the aromatic hydrocarbons. The yields do not much depend on the nature of the aromatic hydrocarbon. For practical use in past and future experiments on aromatic hydrocarbons, an empirical value is given, allowing the estimation of the total concentration of HO(2) radicals formed at 40 Torr He in the presence of around [O(2)] = 1 × 10(17)cm(-3) as a function of the 248 nm excitation energy: [HO(2)]/[aromatic hydrocarbon] ≈ 2 × 10(-6) × E(2) (with E in mJ cm(-2)).