ABSTRACT
Circularly polarized light (CPL) is an inherently chiral entity and is considered one of the possible deterministic signals that led to the evolution of homochirality. While accumulating examples indicate that chirality beyond the molecular level can be induced by CPL, not much is yet known about circumstances where the spin angular momentum of light competes with existing molecular chiral information during the chirality induction and amplification processes. Here we present a light-triggered supramolecular polymerization system where chiral information can both be transmitted and nonlinearly amplified in a "sergeants-and-soldiers" manner. While matching handedness with CPL resulted in further amplification, we determined that opposite handedness could override molecular information at the supramolecular level when the enantiomeric excess was low. The presence of a critical chiral bias suggests a bifurcation point in the homochirality evolution under random external chiral perturbation. Our results also highlight opportunities for the orthogonal control of supramolecular chirality decoupled from molecular chirality preexisting in the system.
ABSTRACT
Introduction of asymmetry into a supramolecular system via external chiral stimuli can contribute to the understanding of the intriguing homochirality found in nature. Circularly polarized light (CPL) is regarded as a chiral physical force with right- or left-handedness. It can induce and modulate supramolecular chirality due to preferential interaction with one enantiomer. Herein, this review focuses on the photon-to-matter chirality transfer mechanisms at the supramolecular level. Thus, asymmetric photochemical reactions are reviewed, and the creation of a chiral bias upon CPL irradiation is discussed. Furthermore, the possible mechanisms for the amplification and propagation of the bias into the supramolecular level are outlined based on the nature of the photochromic building block. Representative examples, including azobenzene derivatives, polydiacetylene, bicyclic ketone, polyfluorenes, Cn -symmetric molecules, and inorganic nanomaterials, are presented.
Subject(s)
Nanostructures , Photons , StereoisomerismABSTRACT
This study investigates two questions: first, how individuals with high-intelligence allocate cognitive resources while solving linguistic, mathematical and visuo-spatial tasks with varying degree of difficulty as compared to individuals with low intelligence? Second, how to distinguish between high and low intelligent individuals by analyzing pupil dilation and eye blink together? We measured the response time, error rates along with pupil dilation and eye blink rate that indicate resource allocation. We divided the whole processing into three stages namely: pre-stimuli (5s prior to stimuli onset), during stimuli and post stimuli (until 5s after the response) for better assessment of preparation and resource allocation strategies. Individuals with high intelligence showed greater task evoked pupil dilation, decreased eye blink with less response time and error rates during-stimuli stage (processing) of tough linguistic and visuo-spatial tasks but not during mathematical tasks. The finding suggests that individuals with high intelligence allocate more resources if the task demands are high else they allocate less resources. Greater pre-stimuli pupil dilation and increased eye blink of high intelligent individuals in all tasks indicated their attentiveness and preparedness. The result of our study shows that individuals with high intelligence are more attentive and flexible in terms of altering the resource allocation strategy according to task demand. Eye-blinks along with pupil dilation and other behavioral parameters can be reliably used to assess the intelligence of an individual and the analysis of pupil dilation and blink rate at pre-stimuli stage can be crucial in distinguishing individuals with varying intelligence.