Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Prolonged tamoxifen exposure selects a breast cancer cell clone that is stable in vitro and in vivo

The effects of long-term tamoxifen exposure on cell growth and cell cycle kinetics were compared between oestrogen receptor (ER)-positive (MCF-7) and ER-negative (MDA-MB-231) cell lines. In the MCF-7 cell line, prolonged tamoxifen exposure (0.5 mumol/l for > 100 days) blocked cells in G0-G1 of the cell cycle, and slowed the doubling time of cells from 30 to 59 h. These effects corresponded to an increase in the cellular accumulation of tamoxifen over time [mean area under concentration curve (AUC) = 77.92 mumoles/10(6)/cells/day]. In contrast, in the MDA-MB-231 cell line, long-term tamoxifen exposure had no obvious effect on the doubling time, and reduced cellular tamoxifen accumulation (mean AUC = 50.50 mumoles/10(6)/cells/day) compared to the MCF-7 cells. Flow cytometric analysis of MDA-MB-231 cells demonstrated that a new tetraploid clone emerged following 56 days of tamoxifen exposure. Inoculation of the MDA-MB-231 tetraploid clone and MDA-MB-231 wildtype cells into the opposite flanks of athymic nude mice resulted in the rapid growth of tetraploid tumours. The tetraploid tumours maintained their ploidy following tamoxifen treatment for nine consecutive serial transplantations. Histological examination of the fifth transplant generation xenografts revealed that the tetraploid tumour had a 25-30 times greater mass, area of haemorrhage and necrosis, a slightly higher mitotic index and was more anaplastic than the control neoplasm. The control wildtype MDA-MB-231 tumours maintained a stable ploidy following tamoxifen treatment until the eighth and ninth transplantation, when a tetraploid population appeared, suggesting that tamoxifen treatment may select for this clone in vivo. These studies suggest that prolonged tamoxifen exposure may select for new, stable, fast growing cell clones in vitro as well as in vivo.     

Optimal power control for Rayleigh-faded multiuser systems with outage constraints

How can we achieve the conflicting goals of reduced transmission power and increased capacity in a wireless network, without attempting to follow the instantaneous state of a fading channel? In this paper, we address this problem by jointly considering power control and multiuser detection (MUD) with outage-probability constraints in a Rayleigh fast-fading environment. The resulting power-control algorithms (PCAs) utilize the statistics of the channel and operate on a much slower timescale than traditional schemes. We propose an optimal iterative solution that is conceptually simple and finds the minimum sum power of all users while meeting their outage targets. Using a derived bound on outage probability, we introduce a mapping from outage to average signal-to-interference ratio (SIR) constraints. This allows us to propose a suboptimal iterative scheme that is a variation of an existing solution to a joint power control and MUD problem involving SIR constraints. We further use a recent result that transforms complex SIR expressions into a compact and decoupled form, to develop a noniterative and computationally inexpensive PCA for large systems of users. Simulation results are presented showing the closeness of the optimal and mapped schemes, speed of convergence, and performance comparisons.