Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps: Novel structure and reactivity features of chromium complexed arene diradical species

The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene–alkyne coupling to generate an enyne–ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored.     

Effect of low intensity laser interaction with human skin fibroblast cells using fiber-optic nano-probes

Over the past forty years, many efforts have been devoted to study low power laser light interactions with biological systems. Some of the investigations were performed in-vitro, on bulk cell populations. Our present work was undertaken to apply specially engineered fiber-optic based nano-probes for the precise delivery of laser light on to a single cell and to observe production of low power laser light induced reactive oxygen species (ROS). A normal human skin fibroblast (NHF) cell line was utilized in this investigation and the cells were irradiated under two different schemes of exposure: (1) an entire NHF cell population within a Petri dish using a fan beam methodology, and (2) through the precise delivery of laser energy on to a single NHF cell using fiber-optic nano-probe. Photobiostimulative studies were conducted through variation of laser intensity, exposure time, and the energy dose of exposure. Laser irradiation induced enhancement in the rate of cell proliferation was observed to be dependent on laser exposure parameters and the method of laser delivery. The total energy dose (fluence) had a greater influence on the enhancement in the rate of cellular proliferation than compared to laser intensity. The enhancement in the growth rate was observed to have a finite life-time of several days after the initial laser exposure. Fluorescent life-time imaging of ROS was performed during the nano-based single cell exposure method. The kinetics of ROS generation was found to depend strongly on the laser fluence and not on the laser intensity.     

Enhanced shape-selective recognition of anion guests through complexation-induced organization of porphyrin hosts

We present a fortuitous discovery of enhanced shape-selective recognition of anion guests that stems from a complexation-induced conformational change in porphyrin hosts upon anion binding. Porphyrin hosts reported here exist in a conformation that is not favorable to guest binding. Anions that bind strongly are those that can induce a conformational change in the host to allow guest binding. Furthermore, guests that mimic the shape of the newly formed pocket bind the strongest.     

The electric field induced by light can explain cellular responses to electromagnetic energy: a hypothesis of mechanism

When cells are irradiated with visible and near-infrared wavelengths a variety of stimulatory effects are observed in their metabolism. To explain the observed light effects, researchers try to identify the chromophores that are involved in the processes. However, the mechanism of light absorption by a chromophore does not explain many of the experimental observations and therefore the primary mechanism for cellular light responses remains unproven. In addition to the ability of photons to produce electronic excitation in chromophores, light induces a wave-like alternating electric field in a medium that is able to interact with polar structures and produce dipole transitions. These dipole transitions are analyzed in the present article at different cellular and biochemical levels, leading to the proposal that the primary mechanism for the observed light effects is related to the light-induced electric field.     

Reflection of plane waves from the boundary of a pre-stressed compressible elastic half-space

The effect of pre-stress on the propagation and reflection ofplane waves in an incompressible isotropic elastic half-spacehas been examined recently by the authors (Ogden & Sotiropoulos,1997). In the present paper the corresponding analysis for compressiblematerials is detailed. In the two-dimensional context consideredfor incompressible materials the (homogeneous) plane waves werenecessarily shear waves. By contrast, in the compressible contextpure shear waves can propagate only in specific directions inthe considered principal plane and, in a general direction,a quasi-shear wave may be accompanied by a quasi-longitudinalwave, as is the case in the anisotropic linear theory. The dependenceof the (in-plane) slowness section on the pre-stress (and finitedeformation) and on the choice of constitutive law is elucidated.This information is used to determine the reflection coefficientsfor reflection of either a (quasi-) shear wave or a (quasi-)longitudinal wave from the boundary of the half-space and tocharacterize the different cases which arise depending on thegeometry of the slowness section. The theoretical results are illustrated by numerical calculationsfor the range of possible types of behaviour with referenceforms of strain-energy function and different states of finitedeformation and to the question of stability of the half-space.