Temperature dependence of kinetics of triplet formation in phenazine: analysis by analogue computer

The temperature dependence of kinetic parameters of triplet phenazine have been determined by analysis of transient response to photoexcitation. The analogue computer used in the analysis is described.     

Transient nutations of photoelectrons from alkali metal anions

Transient nutations of the magnetization of photoelectrons ejected from rubidium and cesium anions are described. The nature of the nutations requires that the time between photoexcitation and appearance of the photoelectron is less than ≈10^?7 s.     

6-Aryl-1-azabicyclo [5.4.0] undecanes

Some 6-aryl-6-hydroxy-l-azabicyclo[5.4.0]undecanes and their esters were synthesized as potential cardiovascular agents and analgetics of the proheptazine type, respectively. Also, 6-aryl-1-azabicyclo[5.4.0]undecanes were prepared as rigid structures related to the phenethylamine CNS stimulants.     

Homology of Littlewood complexes

Let $V$ be a symplectic vector space of dimension $2n$ . Given a partition $\lambda $ with at most $n$ parts, there is an associated irreducible representation $\mathbf{{S}}_{[\lambda ]}(V)$ of $\mathbf{{Sp}}(V)$ . This representation admits a resolution by a natural complex $L^{\lambda }_{\bullet }$ , which we call the Littlewood complex, whose terms are restrictions of representations of $\mathbf{{GL}}(V)$ . When $\lambda $ has more than $n$ parts, the representation $\mathbf{{S}}_{[\lambda ]}(V)$ is not defined, but the Littlewood complex $L^{\lambda }_{\bullet }$ still makes sense. The purpose of this paper is to compute its homology. We find that either $L^{\lambda }_{\bullet }$ is acyclic or it has a unique nonzero homology group, which forms an irreducible representation of $\mathbf{{Sp}}(V)$ . The nonzero homology group, if it exists, can be computed by a rule reminiscent of that occurring in the Borel–Weil–Bott theorem. This result can be interpreted as the computation of the “derived specialization” of irreducible representations of $\mathbf{{Sp}}(\infty )$ and as such categorifies earlier results of Koike–Terada on universal character rings. We prove analogous results for orthogonal and general linear groups. Along the way, we will see two topics from commutative algebra: the minimal free resolutions of determinantal ideals and Koszul homology.     

Combined experimental and theoretical study on aromatic hydroxylation by mononuclear nonheme iron(IV)-oxo complexes

The hydroxylation of aromatic compounds by mononuclear nonheme iron(IV)-oxo complexes, [FeIV(Bn-tpen)(O)]2+ (Bn-tpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine) and [FeIV(N4Py)(O)]2+ (N4Py=N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been investigated by a combined experimental and theoretical approach. In the experimental work, we have performed kinetic studies of the oxidation of anthracene with nonheme iron(IV)-oxo complexes generated in situ, thereby determining kinetic and thermodynamic parameters, a Hammett rho value, and a kinetic isotope effect (KIE) value. A large negative Hammett rho value of -3.9 and an inverse KIE value of 0.9 indicate that the iron-oxo group attacks the aromatic ring via an electrophilic pathway. By carrying out isotope labeling experiments, the oxygen in oxygenated products was found to derive from the nonheme iron(IV)-oxo species. In the theoretical work, we have conducted density functional theory (DFT) calculations on the hydroxylation of benzene by [FeIV(N4Py)(O)]2+. The calculations show that the reaction proceeds via two-state reactivity patterns on competing triplet and quintet spin states via an initial rate determining electrophilic substitution step. In analogy to heme iron(IV)-oxo catalysts, the ligand is noninnocent and actively participates in the reaction mechanism by reshuttling a proton from the ipso position to the oxo group. Calculated kinetic isotope effects of C6H6 versus C6D6 confirm an inverse isotope effect for the electrophilic substitution pathway. Based on the experimental and theoretical results, we have concluded that the aromatic ring oxidation by mononuclear nonheme iron(IV)-oxo complexes does not occur via a hydrogen atom abstraction mechanism but involves an initial electrophilic attack on the pi-system of the aromatic ring to produce a tetrahedral radical or cationic sigma-complex.     

Use of in-tube sorptive extraction techniques for determination of benzene, toluene, ethylbenzene and xylenes in soft drinks

A comparison is made between static headspace analysis and headspace solid-phase dynamic extraction (HS-SPDE) for the quantitative determination of trace level BTEX solvents (benzene, toluene, ethylbenzene and o-, m-, and p-xylene) in soft drinks. Two non-polar extraction phases were investigated for SPDE using an automated sampler with a gas-tight syringe equipped with a special needle coated on the inside with the extraction phase. Following adsorption onto the phase, the analytes were thermally desorbed directly into a GC-MS. The techniques were optimised and evaluated by analysis of spiked soft drink samples. The use of the SPDE device gave comparable results to the static headspace method, with lower detection limits for some compounds, and also offers advantages for applications where lower temperatures are preferred.     

Large-volume sample stacking with polarity switching for the analysis of bacteria by capillary electrophoresis with laser-induced fluorescence detection

Capillary electrophoresis has been utilized for the rapid analysis of bacteria under specific experimental conditions. In this work, a method of large-volume sample stacking with polarity switching was evaluated for the analysis of bacteria by capillary electrophoresis with laser-induced fluorescence detection in order to enhance the detection sensitivity. The results indicated that the proposed method is not only effective for the focusing of bacterial cells, but also for the separation of mixtures of bacteria. With the optimized conditions, an enhancement factor of around 60-fold was obtained when long sample plug (up to 39.6% of capillary volume) was injected. Moreover, with the help of such stacking method, single, sharp, intense peak with high efficiency was observed without multiple peaks attributable to irregular clusters and aggregates of bacterial cells. This simple stacking approach appears to be promising as a rapid sterility test in various fields of applications.     

Racemic versus enantiopure alanine on Cu(110): an experimental study

The adsorption of racemic alanine on the Cu(110) surface has been compared to that of enantiopure alanine using low-energy electron diffraction (LEED), reflection absorption infrared spectroscopy (RAIRS), and scanning tunneling microscopy (STM). No evidence of chiral resolution at the surface was observed for the racemic system, indicating that the formation of separate enantiopure areas is not preferred. Also, in contrast to the enantiopure system, no chirally organized phase was observed for the racemic system. LEED shows that both systems display a common (3 x 2) phase at high coverage. However, the pathway and kinetic barriers to this phase differ markedly for the racemic and the enantiopure systems, with the racemic (3 x 2) appearing at a temperature that is more than 100 K below that required for the enantiopure system. In addition, we report intriguing complexities for the (3 x 2) LEED structure that is ubiquitous in amino acid/Cu(110) systems. First, a common (3 x 2) pattern with a zigzag distortion can be associated with both the racemic and enantiopure systems. For the racemic system, the coverage can be increased further to give a "true" (3 x 2) LEED pattern, which is a transformation that is impossible to enact for the enantiopure system. Most importantly, STM images of the "distorted" and "true" (3 x 2) structures created in the racemic system show subtle differences with neither arrangement being fully periodic over distances greater than a few molecules. Thus, the (3 x 2) phase appears to be more complicated than at first indicated and will require more complex models for a full interpretation.