Slow quenching for a one-dimensional kinetic Ising model: Residual energy and domain growth

A one-dimensional kinetic Ising model with Glauber dynamics subjected to a slow continuous quench to zero temperature is studied. For a rather general class of cooling schemes, described by a time-dependent temperatureT(t), the mean domain sizeL(t) is calculated along with the residual energye _res (r) as a function of the cooling rater. If the attempt frequency =₀ exp(–/kT), entering into the transition rates, is temperature dependent (i.e., the barrier is non-zero), the asymptotic growth ofL(t) is given byL()–L(t)~exp[–/kT(t)]. For this case the residual energy exhibits a power-law behaviore _res(r) ~r ^{/2(1 + )} forr small, where =4J/ andJ is the nearest neighbor coupling constant. For =0 and for certain cooling schemes the residual energy is zero andL(t)~t1/2, independent ofr.     

Simultaneous analysis of oxidized and reduced glutathione in cell extracts by capillary zone electrophoresis

Glutathione (GSH) and glutathione disulfide (GSSG) levels in cells constitute a thiol redox system. They can be used as an indicator of oxidative stress of the cell. In this study, a capillary zone electrophoresis (CZE) method is described that enables quantitation of GSH and GSSG from cellular extracts. The CZE buffer used was 20 mM ammonium acetate containing 5% (v/v) acetic acid at pH 3.1 in conjunction with a polybrene coated capillary operated in reverse polarity mode. Effects of different acids used to prepare cell samples were investigated on CZE performance. The acids include meta phosphoric acid (MPA), trichloroacetic acid (TCA), phosphoric acid (PA) and sulfosalicylic acid (SSA) and are used to stabilize GSH and GSSG before performing CZE analysis. The method features a limit of detection of 4 microM and a limit of quantitation of 12 microM for both GSSG and GSH and recoveries of 94% for GSH and 100% for GSSG. Quantitative analysis of GSSG and GSH in HaCaT cell extracts (5% SSA, w/v) was performed with this method and changes in the ratio of GSH to GSSG in N-ethylmaleimide treated cell sample was observed by comparing with control cell samples.     

Generalizations of the neumann system a curve-theoretical approach-part I

The following observation, due to E. Trubowitz, illustrates an intimate relationship between spectral theory and Hamiltonian mechanics in the presence of constraints. Let q(s) be a real periodic function such that the Hill operator, has only a finite number g^R of simple eigenvalues. There exist g^R + 1 periodic eigenfunctions x₁,…, x and corresponding eigenvalues a₁,…, a of L such that where y_r = dx_r/ds. The equations Lx_r = a_rx_r, r = 1,…,g_R+1, make up the classical Neumann system, a system of harmonic oscillators constrained to the unit sphere. H. Flaschka obtained similar results about the Neumann system from a more general point of view. His assumption, that there exists an operator of odd order that commutes with L, leads to algebraic curve theory by the method of Krichever and from there to the Neumann formulas above. The familiar Lax pairs, the constants of motion and the quadrics of the Neumann system emerge as consequences of the Riemann-Roch theoreni. The existence of isospectral deformations of L, the Korteweg de-Vries hierarchy of the soliton equations, underlies the complete integrability of the Neumann system. This paper extends Flaschka's techniques, replacing L by an operator of order n 2 2. Higher Neumann systems are defined in a way that leads naturally to interesting symplectic manifolds, Lax pairs and integrals of motion. C. Tomei, using scattering theory, obtained some of our n = 3 formulas.     

Massenspektrometrische Beobachtungen und chemische Transportexperimente mit den Systemen VCl3/Al2Cl6 und VCl2/Al2Cl6

Mass Spectroscopic Observations and Chemical Transport Experiments with the Systems VCl₃/Al₂Cl₆ and VCl₂/Al₂Cl₆ By mass spectrometry the equilibrium VCl_3,s + 0.5 Al₂Cl_6,g ? VAlCl_6,g has been determined: ΔH°(298) = 25.6(±0.5) kcal; ΔS°(298) = 23.0(±3) cal/K, ΔCp (assumed) = ?4 cal/K. This is approximately in agreement with results determined by ligand field spectroscopy by ANUNDSKÅS and ØYE (A. and Ø.). For the dimerization of VCl_3,g values for ΔH and ΔS have been derived. The molecule VAl₂Cl₉ assumed by A. and Ø. could not been observed by mass spectrometry. For the VCl₂/Al₂Cl₆ complex, observed by chemical transport, A. and Ø. give the formula VAl₃Cl₁₁. This molecule could not been observed by mass spectrometry. This suggests a smaller concentration, compared with the results of A. and Ø. Stabilization of VCl_2,s (by metal-nietal-bonds) shifts the reaction to the left, whith explains the lower complex concentration as well as the larger molecular weight of the complex. With chlorides stabilized by stronger metal-metal bonds (MoCl₃, MoCl₂, Nb₃Cl₈) AlCl₃ complexes are not formed in observable concentrations. The chemical transport of VCl₂ with Al₂Cl₆ needs relatively high temperatures (973 → 873 K). In this case the addition of SiCl₄ hinders the attack of the quartz ampoule by Al₂Cl₆. Using a VCl₃ + VCl₂ mixture, VCl₃ is transported by Al₂Cl₆ (673 → 623 K) into the colder region. If afterwords the ampoule is reversed, VCl₃ again moves into the colder region, but the thermal decomposition of VCl₃ at the same time causes that a VCl₂-residue remains in the hot region.     

Gas-phase derivatization of [C3H5]+ ions using tandem mass spectrometry methods A13C labelling study

The study of specifically ¹³C-labelled precursors sheds further light on the gas-phase chemistry of allyl and 2-propenyl cations. It is demonstrated that both species are formed from allyl and 2-propenyl bromide upon 70 eV electron impact ionization without skeletal reorganization. Gas-phase derivatization of the [C₃ H₅]⁺ ions with benzene facilitates, as suggested and observed earlier, the distinction of the two isomers using collision-induced dissociation of the Wheland complexes (or isomers thereof). The ¹³C labelling data clearly demonstrate that 64% of allyl cations survive the derivatization while 36% isomerize to 2-phenylpropyl cations; the latter are also formed via the reaction of 2-propenyl cation with benzene, protonation of α-methylstyrene and water loss from protonated 2-phenyl-2-propanol, respectively. Unimolecular loss of C₂H₄ from protonated allylbenzene proceeds via two competing reaction channels: one involves heterolysis of 1-phenylpropyl cations (～30%); the major pathway (～70%), however, involves decomposition via propylene benzenium ions.     

Quantification of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in the picogram/liter range in water of the river Elbe

Sampling and determination of dissolved and particlebound PCBs and HCB in the river Elbe are described. A new filtration/adsorption unit for sampling of dissolved lipophilic contaminants was developed. The detection limit for dissolved PCBs and HCB was 5 pg/l. The data show that more than 98% of the PCBs and of HCB in the water of the river Elbe are particle-bound.     

Tributylgermanium hydride as a replacement for tributyltin hydride in radical reactions

Tributylgermanium hydride (Bu(3)GeH) can be used as an alternative to tributyltin hydride (Bu(3)SnH) as a radical generating reagent with a wide range of radical substrates. Tributylgermanium hydride has several practical advantages over tributyltin hydride, e.g. low toxicity, good stability and much easier work-up of reactions. The reagent can be easily prepared in good yield and stored indefinitely. Suitable substrates include iodides, bromides, activated chlorides, phenyl selenides, tert-nitroalkanes, thiocarbonylimidazolides and Barton esters. Alkyl, vinyl and aryl radicals can be generated in radical reactions including reduction and cyclisation processes. Common radical initiators such as ACCN and triethylborane can be used. The slower rate of hydrogen abstraction by carbon-centred radicals from Bu(3)GeH as compared to Bu(3)SnH facilitates improved cyclisation yields. Polarity reversal catalysis (PRC) with phenylthiol can be used in reactions which generate stable radical intermediates which will not abstract hydrogen from Bu(3)GeH.     

Energy relaxation in aϕ 4 with long range interactions

We investigate the influence of long range interactions on the relaxation behaviour of a lattice model with an on-site potential of ⁴-type and infinite range harmonic interactions. For finite number of particlesN, it is shown that the autocorrelation functions <E _n(t)E _n > of the fluctuations of the one-particle energiesE _n(t) decays exponentially. The corresponding relaxation time is proportional toN and is given by (T, N) =N₀(T). The temperature dependent time scale ₀ can explicitly be related to the dynamics of a one-particle correlator of the noninteracting system. The results are derived using Mori-Zwanzig projection formalism. The corresponding memory kernel is calculated within a mode coupling approximation and by a perturbative approach. Both results agree in leading order in 1/N. It is speculated that any interaction of range generates a timescale .