Generalizing Rosenbluth's Algorithm to Include Along‐the‐Chain Intramolecular Energies

We incorporate the Boltzmann factors for inter‐monomer bending energy into the monomer growth direction choice in Rosenbluth's algorithm to model chains of arbitrary nearest‐neighbor rigidity. This allows for the consideration of compact (bent state lower in energy), free (straight and bent state equal in energy), or extended chains (bent state higher). We validate against, and compare to, various other results, showing very good agreement with known results for short chains and demonstrate the ability to model chains up to 500 segments long, far beyond the length at which the normal Rosenbluth method becomes unstable for reasonable nonzero bending energies. This approach is easily generalizable both to other energies determinable during chain growth, for example, polymers composed of more than one type of monomer with differing monomer interaction energies, as well as to other chain production algorithms. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1684–1691     

Predicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigation

Photochemical oxidative cyclodehydrogenation reactions are a versatile class of aromatic ring‐forming reactions. They are tolerant to functional group substitution and heteroatom inclusion, so can be used to form a diverse range of extended polyaromatic systems by fusing existing ring substituents. However, despite their undoubted synthetic utility, there are no existing models—computational or heuristic—that predict the outcome of photocyclisation reactions across all possible classes of reactants. This can be traced back to the fact that “negative” results are rarely published in the synthetic literature and the lack of a general conceptual framework for understanding how photoexcitation affects reactivity. In this work, we address both of these issues. We present experimental data for a series of aromatically substituted pyrroles and indoles, and show that quantifying induced atomic forces upon photoexcitation provides a powerful predictive model for determining whether a given reactant will photoplanarise and hence proceed to photocyclised product under appropriate reaction conditions. The propensity of a molecule to photoplanarise is related to localised changes in charge distribution around the putative forming ring upon photoexcitation. This is promoted by asymmetry in molecular structures and/or charge distributions, inclusion of heteroatoms and ethylene bridging and well‐separated or isolated photocyclisation sites.     

Activation of muscarinic acetylcholine receptors elicits pigment granule dispersion in retinal pigment epithelium isolated from bluegill

Background

In fish, melanin pigment granules in the retinal pigment epithelium disperse into apical projections as part of the suite of responses the eye makes to bright light conditions. This pigment granule dispersion serves to reduce photobleaching and occurs in response to neurochemicals secreted by the retina. Previous work has shown that acetylcholine may be involved in inducing light-adaptive pigment dispersion. Acetylcholine receptors are of two main types, nicotinic and muscarinic. Muscarinic receptors are in the G-protein coupled receptor superfamily, and five different muscarinic receptors have been molecularly cloned in human. These receptors are coupled to adenylyl cyclase, calcium mobilization and ion channel activation. To determine the receptor pathway involved in eliciting pigment granule migration, we isolated retinal pigment epithelium from bluegill and subjected it to a battery of cholinergic agents.

Results

The general cholinergic agonist carbachol induces pigment granule dispersion in isolated retinal pigment epithelium. Carbachol-induced pigment granule dispersion is blocked by the muscarinic antagonist atropine, by the M₁ antagonist pirenzepine, and by the M₃ antagonist 4-DAMP. Pigment granule dispersion was also induced by the M₁ agonist 4-[N-(4-chlorophenyl) carbamoyloxy]-4-pent-2-ammonium iodide. In contrast the M₂ antagonist AF-DX 116 and the M₄ antagonist tropicamide failed to block carbachol-induced dispersion, and the M₂ agonist arecaidine but-2-ynyl ester tosylate failed to elicit dispersion.

Conclusions

Our results suggest that carbachol-mediated pigment granule dispersion occurs through the activation of M_odd muscarinic receptors, which in other systems couple to phosphoinositide hydrolysis and elevation of intracellular calcium. This conclusion must be corroborated by molecular studies, but suggests Ca²⁺-dependent pathways may be involved in light-adaptive pigment dispersion.

     

The PyPES library of high quality semi‐global potential energy surfaces

In this article, we present a Python‐based library of high quality semi‐global potential energy surfaces for 50 polyatomic molecules with up to six atoms. We anticipate that these surfaces will find widespread application in the testing of new potential energy surface construction algorithms and nuclear ro‐vibrational structure theories. To this end, we provide the ability to generate the energy derivatives required for Taylor series expansions to sixth order about any point on the potential energy surface in a range of common coordinate systems, including curvilinear internal, Cartesian, and normal mode coordinates. The PyPES package, along with FORTRAN, C, MATLAB and Mathematica wrappers, is available at http://sourceforge.net/projects/pypes-lib . © 2015 Wiley Periodicals, Inc.