Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Stochastic analysis in life office management: applications to large annuity portfolios

The paper deals with the riskiness analysis for a large portfolio of life annuities. By means of the limiting distribution of the present value of the portfolio, in the first part of the paper a model for evaluating the investment and the projection risks is presented. In the second part, with regard to the investment risk's effects, the insolvency risk is measured considering the cumulative probability distribution function of the discounted average cost per policy. Copyright © 2003 John Wiley & Sons, Ltd.     

The Downs-Thomson Paradox: Existence, Uniqueness and Stability of User Equilibria

Consider a network where two routes are available for users wishing to travel from a source to a destination. On one route (which could be viewed as private transport) service slows as traffic increases. On the other (which could be viewed as public transport) the service frequency increases with demand. The Downs-Thomson paradox occurs when improvements in service produce an overall decline in performance as user equilibria adjust. Using the model proposed by Calvert [10], with a ⋅|M|1 queue corresponding to the private transport route, and a bulk-service infinite server queue modelling the public transport route, we give a complete analysis of this system in the setting of probabilistic routing. We obtain the user equilibria (which are not always unique), and determine their stability.AMS subject classification: 60K30, 90B15, 90B20, 91A10, 91A13This revised version was published online in June 2005 with corrected coverdate     

Model-dependent nature of blowtorch effect on the escape and equilibration rates

We analyze the relaxation behavior of a bistable system when the background temperature profile is inhomogeneous due to the presence of a localized hot region (blowtorch) on one side of the potential barrier. Since the diffusion equation for inhomogeneous medium is model-dependent, we consider two physical models to study the kinetics of such system. Using a conventional stochastic method, we obtain the escape and equilibration rates of the system for the two physical models. For both models, we find that the hot region enhances the escape rate from the well where it is placed while it retards the escape rate from the other well. However, the value of the escape rate from the well where the hot region is placed differs for the two models while that of the escape rate from the other well is identical for both. This work, for the first time, gives a detailed report of the similarities and differences of the escape rates and, hence, exposes the common and distinct features of the two known physical models in determining the way the bistable system relaxes. Received 25 September 2001     

Transient behavior of subthreshold characteristics of fullydepleted SOI MOSFETs

It has been found that the subthreshold currents of fully depleted silicon-on-insulator (SOI) MOSFETs show a transient behavior under certain front-gate and back-gate voltage conditions. The cause of this anomaly is explained, and applications for the phenomenon are pointed out. Particularly, a simple way to measure the silicon film thickness is suggested     

AFM, SEM and GIXRD studies of thin films of red polycarbazolyldiacetylenes

In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings.