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First isomeric yield ratio measurements by direct ion counting and implications for the angular momentum of the primary fission fragments
2018
We report the first experimental determination of independent isomeric yield ratios using direct ion counting with a Penning trap, which offered such a high resolution in mass that isomeric states could be separated. The measurements were performed at the Ion Guide Isotope Separator On-Line (IGISOL) facility at the University of Jyvaskyla. The isomer production ratios of Ge-81, Y-96,Y-97 Sn-128(,1)30, and Sb-129 in the 25-MeV proton-induced fission of U-na(t) and Th-232 were studied. Three isomeric pairs (Ge-81, Y-96, and Sb-129) were measured for the first time for the U-na(t)(p, f) reaction, while all the reported yield ratios for the Th-232(p, f) reaction were determined for the first ti…
High‐nuclearity mixed‐valence magnetic clusters : A general solution of the double exchange problem
1996
We report here a general solution of the double‐exchange problem in the high‐nuclearity mixed valence systems containing arbitrary number P of the electrons delocalized over the network of N (P<N) localized spins. The developed approach is based on the successive (chainlike) spin‐coupling scheme and takes full advantage from the quantum angular momentum theory. In the framework of this approach the closed‐form analytical expressions are deduced for the matrix elements of the double exchange interaction, two‐electron transfer, and three‐center interaction that can be referred to as the potential exchange transfer. For the arbitrary nuclearity mixed‐valence systems the matrix elements of all …
Ring splitting of azetidin-2-ones via radical anions
2012
The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage. The preference for beta-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
Surface charge fine tuning of reversed-phase/weak anion-exchange type mixed-mode stationary phases for milder elution conditions.
2015
A series of new mixed-mode reversed-phase/weak anion-exchange (RP/WAX) phases have been synthesized by immobilization of N-undecenyl-3-α-aminotropane onto thiol-modified silica gel by thiol-ene click chemistry and subsequent introduction of acidic thiol-endcapping functionalities of different type and surface densities. Click chemistry allowed to adjust a controlled surface concentration of the RP/WAX ligand in such a way that a sufficient quantity of residual thiols remained unmodified which have been capped by thiol click with either 3-butenoic acid or allylsulfonic acid as co-ligands. In another embodiment, performic acid oxidation of N-undecenyl-3-α-aminotropane-derivatized thiol-modifi…
Nonlinear response of a batch BZ oscillator to the addition of the anionic surfactant sodium dodecyl sulfate.
2007
The response of the Belousov-Zhabotinsy (BZ) system to the addition of increasing amounts of the anionic surfactant sodium dodecyl sulfate (SDS) was monitored at 25.0 degrees C in stirred batch conditions. The presence of SDS in the reaction mixture influences the oscillatory parameters, i.e., induction period and oscillation period, to an extent that depends on the surfactant concentration. The experimental results have shown that the induction period increases slightly on increasing surfactant concentration and, then, a further increase in the [SDS] leads to an enhancement while the oscillation period increases monotonously on increasing SDS concentration. It has been proposed that the re…
N-Propyl-N′-2-pyridylurea-modified silica as mixed-mode stationary phase with moderate weak anion exchange capacity and pH-dependent surface charge r…
2018
Herein, we present a novel silica-based stationary phase modified with N-propyl-N'-2-pyridylurea selector. Due to the weakly basic properties of the pyridine selector and the presence of residual silanols after selector immobilization, a zwitterionic surface with a pI observed at approximately pH 5.5 was measured by electrophoretic light scattering in pH-dependent ζ-potential determinations. The capability of the new N-propyl-N'-2-pyridylurea-modified silica to serve as mixed-mode stationary phase was investigated. For this purpose, it was characterized under RP and HILIC conditions using test mixtures. Subsequent classification of this stationary phase in comparison to in-house and commerc…
The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts
2005
The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…
Experimental investigation of anion-π interactions : Applications and biochemical relevance
2015
Chemical communications 52(9), 1778 - 1795(2016). doi:10.1039/C5CC09072E
Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies
2018
Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Structures of complexes with Cl−, Br−, NO3 −, SO4 2− and AcO−, supported by computational studies, show how the binding site can adapt to accommodate these anions. 1H NMR binding studies revealed exception…
Burrowing behaviour affects Paraergasilus rylovi abundance in Anodonta piscinalis.
2006
Burrowing depth may affect predation rate, feeding ability and reproduction in bivalve clams. We studied the effect of burrowing depth on the abundance of the ergasilid Paraergasilus rylovi in the freshwater bivalve clam Anodonta piscinalis. We transplanted uninfected clams to a lake where they were allowed to choose their preferred burrowing depth, and were exposed naturally to copepodids of the parasite. There was a significant positive correlation between proportionate burrowing depth (PBD) and the abundance of P. rylovi at the end of the 17-day experiment, the deeper-burrowed clams harbouring more P. rylovi. Original PBD (0%, 50%, 100%) did not influence the final PBD or parasite abunda…