Control of Chromophore Symmetry by Positional Isomerism of Peripheral Substituents

The first example of the control of porphyrinoid chromophore symmetry based on the positional isomerism of peripheral substituents has been achieved by preparing tetraazaporphyrins (TAPs) with C_4h, D_2h, C_2v, and C_s symmetry due to the relative arrangement of peripheral tert‐butylamino and cyano groups as push and pull substituents, respectively. The four structural isomers were successfully isolated and characterized by ¹H NMR spectroscopy and X‐ray crystallography. The band morphology in the Q‐band region varies depending on the molecular symmetry due to the significant perturbation introduced into the chromophore by the push and pull substituents. The C_4h and C_2v isomers exhibit a single Q band, whereas the Q bands of the D_2h and C_s isomers show a marked splitting. The magnetic circular dichroism spectra indicate that the push–pull TAPs retain the properties of the 16‐membered 18π‐electron perimeter generally observed for porphyrinoids. Theoretical calculations have demonstrated that the perturbation introduced by the substituents lowers the D_4h symmetry of the parent TAP π‐conjugated system, and this results in significant spectral changes. A novel approach to the fine‐tuning of the spectral properties of porphyrinoids based on changes in the chromophore symmetry is described.     

Copper–Oxygen Dynamics in the Tyrosinase Mechanism

The dinuclear copper enzyme, tyrosinase, activates O₂ to form a (μ-η²:η²-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom.     

Simultaneous kinetic determination of secondary amines and their isomers by a spectrophotometric stopped-flow method based on the formation of dialkyldithiocarbamates

Secondary amines react with carbon disulphide to form stable dialkyldithiocarbamates at high pH in aqueous Triton X-100 solution. The formation rates of dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n-butyl- and diisobutyldithiocarbamates and pyrrolidinedithiocarbamate were measured by a stopped-flow spectrophotometric method. The reaction rates were a function of the pH of the solution and depended on the size and structure of the amines. The rate of isoalkylamines was far slower than that of the n-alkyl analogues. Individual concentrations of amines were determined in a mixture of di-n- and diisopropylamine and in a mixture of diiso- and di-n-butylamine.     

Decomposability in queues with background states

A symmetric queue is known to have a nice property, the so-called insensitivity. In this paper, we generalize this for a single node queue with Poisson arrivals and background state, which changes at completion instants of lifetimes as well as at the arrival and departure instants. We study this problem by using the decomposability property of the joint stationary distribution of the queue length and supplementary variables, which implies the insensitivity. We formulate a Markov process representing the state of the queue as an RGSMP (reallocatable generalized semi-Markov process), and give necessary and sufficient conditions for the decomposability. We then establish general criteria to be sufficient for the queue to possess the property. Various symmetric-like queues with background states, including continuous time versions of moving server queues, are shown to have the decomposability.This author is partially supported by NEC C&C Laboratories.     

Heavy and light traffic in fluid models with burst arrivals

We consider the problem of finding a heavy and light traffic limits for the steady-state workload in a fluid model having a continuous burst arrival process. Such a model is useful for describing (among other things) the packetwise transmission of data in telecommunications, where each packet is approximated to be a continuous flow. Whereas in a queueing model, each arrival epoch,t _n , corresponds to a customer with a service timeS _n , the burst model is different: each arrival epoch,t _n , corresponds to a burst of work, that is, a continuous flow of work (fluid, information) to the system at rate 1 during the time interval [t _n ,t _n +S _n ]. In the present paper we show that the burst and queueing models share the same heavy-traffic limit for work, but that their behavior in light traffic is quite different.Research supported by the Japan Society for the Promotion of Science, during the author's fellowship in Tokyo.Research funded by C & C Information Technology Research Laboratories, NEC, and the International Science Foundation.     

A short and efficient asymmetric synthesis of komaroviquinone

An asymmetric total synthesis of komaroviquinone (1), which is a natural product isolated from Dracocephalum komarovi and shows novel potent trypanocidal activity, was achieved in five steps from the known starting materials. The synthetic route is shorter and more efficient than the reported methods and also useful for the scale-up synthesis.