XUV free-electron laser desorption of NO from graphite (0001)

We report results of femtosecond laser induced desorption of NO from highly oriented pyrolytic graphite using XUV photon energies of hν = 38 eV and hν = 57 eV. Femtosecond pulses with a pulse energy of up to 40 μJ and about 30 fs duration generated at FLASH are applied. The desorbed molecules are detected with rovibrational state selectivity by (1 + 1) REMPI in the A(2)Σ(+) ← X(2)Π γ-bands around λ = 226 nm. A nonlinear desorption yield of neutral NO is observed with an exponent of m = 1.4 ± 0.2. At a fluence of about 4 mJ/cm(2) a desorption cross section of σ(1) = (1.1 ± 0.4) × 10(-17) cm(2) is observed, accompanied with a lower one of σ(2) = (2.6 ± 0.3) × 10(-19) cm(2) observable at higher total fluence. A nonthermal rovibrational population distribution is observed with an average rotational energy of = 38.6 meV (311 cm(-1)), a vibrational energy of = 136 meV (1097 cm(-1)) and an electronic energy of = 3.9 meV (31 cm(-1)).     

Mixed electrolytes in hydrophobic interaction chromatography†

An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins.     

Synthesis of neutral spin-delocalized electron acceptors for multifunctional materials

A new synthetic route to stable spin-delocalized radicals, annelated nitronyl nitroxides, has been developed on the basis of the condensation of benzofuroxan with aryl nitrones. The electronic structure of the resulting radicals was investigated through absorption spectroscopy, EPR, electrochemistry, and computation (DFT-UB3LYP). The annelated radicals exhibit electronic transitions in the near IR (850-900 nm) and are excellent electron acceptors (E(red) approximately 0.0 vs SCE) ideal for the development of multifunctional magnetic materials.     

Electron impact induced fragmentation of aromatic N-alkoxy-imines I. Ring closure in (M-CH2O)+• ions by intramolecular aromatic substitution

Summary N-Butoxy- and N-propoxy-imines derived fromo-,m-, andp-substituted benzaldehydes (X = F, Cl, Br, I) decompose upon electron impact to the respective aldoximes by loss of C _n H_2n and competitivelyvia 1,5-distonic radical cations by loss of CH₂O to 1,3-distonic ions which eliminate H and/or a halogen atom in the course of homolytic aromatic substitution, giving rise to cyclic (M-CH₂O-H)⁺ or (M-CH₂O-X )⁺ ions.Dedicated with warm regards to Prof. Dr.D. Seebach, Zürich, on the occasion of his 60^th birthday     

Homogenous synthesis of 3-allyloxy-2-hydroxypropyl-cellulose in NaOH/urea aqueous system

3-Allyloxy-2-hydroxypropylcelluloses (AHP-celluloses), reactive unsaturated cellulose derivatives, were homogeneously synthesized by the reaction of cellulose with allyl glycidyl ether (AGE) in NaOH/urea aqueous solution. Water-soluble AHP-celluloses with DS_NMR = 0.32–0.67 were prepared from microcrystalline cellulose. The degree of substitution (DS) of AHP-celluloses could be controlled by varying the molar ratio of AGE and NaOH to AGU and the reaction conditions. The structure of AHP-cellulose samples were characterized by means of FT-IR, NMR spectroscopy and size exclusion chromatography. The cellulose ether shows thermoreversible flocculation. Bromination reactions were carried out as subsequent functionalization both to illustrate the reactivity of the allyl function and to determine the DS values.     

Ultra‐Small Plutonium Oxide Nanocrystals: An Innovative Material in Plutonium Science

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO₂) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO₂(NO₃)₂] ? 3 H₂O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO₂ NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO₂ NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO₂ NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements.     

Phase equilibria and excess properties for binary systems in reactive distillation processes Part I. Methyl acetate synthesis

Isothermal vapor–liquid equilibrium (VLE) and excess enthalpy (H^E) data were measured for binary systems required for the design of reactive distillation processes for the methyl acetate production. The isothermal P–x data were measured with the help of a computer-operated static apparatus. A commercial isothermal flow calorimeter was used for the determination of the heats of mixing. Temperature-dependent interaction parameters for the UNIQUAC model were fitted simultaneously to the experimental data from this work and other authors.