Excited state hydrogen bond dynamics: coumarin 102 in acetonitrile-water binary mixtures

The time dependent change in the intermolecular response of solvent molecules following photoexcitation of Coumarin 102 (C102) has been measured in acetonitrile-water binary mixtures. Experiments were performed on mixtures of composition x(CH3CN) = 0.25, 0.50, 0.75, and 1.00. At low water concentrations (x(H2O) < or = 0.25) the solvent response is consistent with previous measurements probing dipolar solvation. With increasing water concentration (x(H2O) > or = 0.50) an additional response is found subsequent to dipolar solvation, exhibited as a rapid gain in the solvent's polarizability on a approximately 250 fs time scale. Monte Carlo simulations of the C102:binary mixture system were performed to quantify the number of hydrogen-bonding interactions between C102 and water. These simulations indicate that the probability of the C102 solute being hydrogen bound with two water molecules, both as donors at the carbonyl site, increases in a correlated fashion with the amplitude of the additional response in the measurements. We conclude that excitation of C102 simultaneously weakens and strengthens hydrogen bonding in complexes with two inequivalently bound waters.     

Robustness of virus removal by protein A chromatography is independent of media lifetime

The robustness of virus clearance with respect to protein A media reuse was demonstrated using media with four matrix chemistries: Protein A immobilized ProSep A, Poros A50, Protein A ceramic Hyper DF and MabSelect SuRe, an alkali resistant protein A ligand. Endogenous retrovirus clearance, step yield, impurity clearance and other performance parameters were evaluated periodically in media cycled up to 300 times. Media lifetime was generally limited by either declining step yield or media fouling. However, clearance of endogenous retrovirus remained in an acceptable range, either increasing or remaining constant. Multiply cycled media were tested for clearance of three viruses (SV40, X-MuLV, and MMV); clearance was comparable to na?ve media. Overall, virus clearance by protein A chromatography appears to be extremely robust with respect to media age.     

Comparison ofβ-decay and Charge-exchange Reactions in Mirror T =2 Nuclei and Isospin Mixing

We have carried out β decay studies of proton rich nuclei in the fp shell at different laboratories.Here we present our recent results on the decay of Tz =-2 nuclei performed at GANIL and compare them with the Charge Exchange reactions on their stable, mirror-partner targets, performed at RCNP. In one of the cases, the 56Zn - 56Fe pair, a strong isospin mixing has been observed. The results are well reproduced in the framework of Shell Model calculations     

Total synthesis of myxovirescin A1

A convergent total synthesis of the antibiotic macrolide myxovirescin A1 (1) is described that is largely based on reagent- and catalyst-controlled transformations. This includes a highly regioselective Negishi reaction of dibromo-alkene 48 with an alkynylzinc reagent, and a palladium catalyzed alkyl-Suzuki coupling of the resulting enyne derivative 12 with the 9-BBN-adduct derived from alkene 61. The latter was obtained via an asymmetric hydrogenation of the chlorinated beta-ketoester 49 and an anti-selective oxyallylation of the functionalized aldehyde 53 as the key steps. The preparation of the bis-borylated allyl-donor 57 used in the oxyallylation step, however, required careful optimization and led to important insights into the nature of the classical hydroborating agent "di(isopinocampheyl)borane (Ipc2BH)". It was unambiguously shown by X-ray crystallography that in the solid state this compound is dimeric, but it is prone to undergo an essentially quantitative mono-deborylation when dissolved in CH2Cl2 or benzene; its composition in ethereal solvents is even more complex as evident from 11B NMR data. Product 71 derived from 12 and 61 was elaborated into the enyne-yne derivative 75, which served as the substrate for an exquisitely selective ring closing alkyne metathesis reaction (RCAM) catalyzed by the molybdenum tris-amido complex 20 activated in situ with CH2Cl2. The resulting cyclic enyne 76 was subjected to a ruthenium catalyzed trans-hydrosilylation/proto-desilylation tandem. Although [Cp*Ru(MeCN)3]PF6 had previously been recommended as catalyst of choice for trans-hydrosilylation reactions of internal alkynes, this complex failed to afford the desired product, whereas its sterically less hindered congener [CpRu(MeCN)3]PF6 permitted the reaction to be performed in appreciable yield, but at the expense of a lower stereoselectivity. AgF-mediated proto-desilylation of the isomeric silanes 79 and 80 followed by cleavage of the remaining acetal protecting groups afforded myxovirescin A1 and its hitherto unknown 14Z-isomer 81, respectively.     

Oxidative and reductive carbodiazenylation of nonactivated olefins

Procedures for the carbodiazenylation of nonactivated olefins with a wide range of aryldiazonium salts have been developed. The azo compounds obtained can serve as valuable precursors for beta-arylamines (carboamination products), beta-amino acids, ketones, and various heterocyclic structures.     

Allylation and vinylation of aryl radicals generated from diazonium salts

Allylation and vinylation of aryl radicals generated from aryl diazonium salts provides rapid and efficient access to chlorinated and brominated derivatives of styrene and allylbenzene. Allyl chlorides were found to be better substrates than bromides due to decreased halogen transfer. Donor- and acceptor-substituted diazonium salts are well tolerated. The products represent important precursors for numerous further transformations.     

Effect of a triaxial nuclear shape on proton tunneling: the decay and structure of 145Tm

Gamma rays deexciting states in the proton emitter 145Tm were observed using the recoil-decay tagging method. The 145Tm ground-state rotational band was found to exhibit the properties expected for an h{11/2} proton decoupled band. In addition, coincidences between protons feeding the 2{+} state in 144Er and the 2{+}-->0{+} gamma-ray transition were detected, the first measurement of this kind, leading to a more precise value for the 2{+} excitation energy of 329(1) keV. Calculations with the particle-rotor model and the core quasiparticle coupling model indicate that the properties of the pi{11/2} band and the proton-decay rates in 145Tm are consistent with the presence of triaxiality with an asymmetry parameter gamma approximately 20 degrees .     

Electronic properties of single-crystal diamonds heavily doped with boron

Single-crystal diamonds with characteristic sizes of 2–7 mm doped with boron in the concentration range 10¹⁹–10²⁰ cm^?3 have been grown by the temperature gradient method at high static pressures. The temperature dependence of the resistance R of the synthesized single crystals has been measured in the range 0.5 K < T < 297 K. An activated dependence R(T) with an activation energy of about 50 meV is observed in the range from room temperature to T ≈ 200 K. At temperatures below approximately 50 K, the temperature dependence of the conductivity for heavily doped crystals is proportional to T ^1/2, which is characteristic of degenerate semiconductors with a high number of defects.     

Features of the transformation of detonation nanodiamonds into onion-like carbon nanoparticles

On the basis of the results of investigations carried out by differential scanning calorimetry, X-ray diffraction, nuclear magnetic resonance, high-resolution transmission electron microscopy, and Raman spectroscopy, a scheme for the transformation of detonation nanodiamonds (which are agglomerates of smaller particles) into onion-like carbon nanoparticles during vacuum annealing is verified. At high temperatures, the transition of an individual nanodiamond occurs in a short period of time and may proceed via an amorphous state.     

η-Cyclopentadienylpalladium(II) complexes: Synthesis, characterization and use for the vinyl addition polymerization of norbornene and the copolymerization with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene

Dinuclear complexes of palladium(II), containing two bridging halogen (Cl or Br) ligands, [NⁿBu₄]₂[(X₅C₆)₂Pd(μ-Cl)₂Pd(C₆X₅)₂] and [(X₅C₆)(L)Pd(μ-Y)₂Pd(C₆X₅)(L)] (X = F, Cl; Y = Cl, Br), readily react with cyclopentadienylthallium, C₅H₅Tl, to give the corresponding air stable half-sandwich, pseudo-trigonal η⁵-cyclopentadienylpalladium complexes, [NⁿBu₄][(η⁵-C₅H₅)Pd(C₆X₅)₂] (X = F 1, Cl 2) and (η⁵-C₅H₅)Pd(C₆X₅)(L) (X = F, L = CNBu^t3, PPh₃4, PMe₂Ph 5, PEt₃6, AsPh₃7, SbPh₃8; X = Cl, L = PMe₂Ph 9, PEt₃10), respectively. With tetraphenylcyclopentadienylthallium, C₅Ph₄HTl or pentabenzylcyclopentadienylthallium, C₅Bn₅Tl (Bn = CH₂Ph) the air stable half-sandwich complexes (η⁵-C₅Ph₄H)Pd(C₆F₅)(AsPh₃), 12 and (η⁵-C₅Bn₅)Pd(C₆F₅)(AsPh₃), 13 are synthesized accordingly. The molecular structures were verified by NMR-spectroscopy, X-ray crystallography (7, 12, 13) and electron impact-mass spectrometry (EI-MS). The precatalysts 4 and 7 can be activated with methylalumoxane (MAO) for the homopolymerization of norbornene (NB) and 5-ethylidene-2-norbornene (ENB) and for the copolymerization of NB with 5-vinyl-2-norbornene (VNB) or ENB with activities of more than 10⁶ g_PNB/(mol_Pd·h). The higher activity of 7/MAO over 4/MAO towards NB homopolymerization was reversed when the olefin-substituted VNB or ENB were added. Then, the more strongly bound PPh₃ ligand of 4 (versus AsPh₃ of 7) can compete with the olefin functionality of VNB or ENB and assume a directing role for the insertion of the ring double bond. As a consequence 4/MAO shows almost the same activity in NB and ENB homopolymerization.