Hammett studies of enantiocontrol by PHOX ligands in Pd-catalyzed allylic substitution reactions

Electronically modified PHOX ligands 3a-e were synthesized to probe the mechanism of the enantioselective palladium-catalyzed allylic alkylation and amination reactions. Alkylation with dimethyl sodiomalonate produced only a small variation in the ee (89.3% to 93.4%), but amination with benzylamine gave a much wider variation in the ee (16.4% to 66.6%). Hammett analysis suggests that the substituents interact more significantly with phosphorus and supports a combined electronic and steric basis for enantioselection. [reaction: see text]     

Modeling the Selectivity of Potassium Channels with Synthetic,Ligand‐Assembled π Slides

A supramolecular ion channel model mediates transmembrane ion transport (shown schematically) with a selectivity topology similar to that of K⁺ channels. This supports the biological significance of flexible arene arrays as selective cation binding sites.     

Damaging Effects of Ultraviolet Radiation on the Cornea

The cornea sits at the anterior aspect of the eye and, like the skin, is highly exposed to ultraviolet radiation (UVR). The cornea blocks a significant proportion of UVB from reaching the posterior structures of the eye. However, UVA can penetrate the full thickness of the cornea, even reaching the anterior portion of the lens. Epidemiological data indicate that UVR is a contributing factor for a multitude of diseases of the cornea including pterygium, photokeratitis, climatic droplet keratopathy and ocular surface squamous neoplasia (OSSN), although the pathogenic mechanisms of each require further elucidation. UVR is a well‐known genotoxic agent, and its effects have been well characterized in organs such as the skin. However, we are only beginning to identify its effects on the cornea, such as the UVR signature C → T and CC → TT transversions identified by sequencing and increased proliferative and shedding rates in response to UVR exposure. Alarmingly, a single low‐dose exposure of UVR to the cornea is sufficient to elicit genetic, molecular and cellular changes, supporting the consideration of using protective measures, such as wearing sunglasses when outdoors. The aim of this review was to describe the adverse effects of UVR on the cornea.     

Triangle-free graphs and completely positive matrices

Central European Journal of Operations Research - Completely positive matrices are matrices that can be decomposed as $$BB^T$$ , where B is an entrywise nonnegative matrix. These matrices have many...     

Regioselective lithiation of II-(arene)chromium tricarbonyl complexes

Chromium tricarbonyl complexes of 3-methoxybenzyl alcohol and related compounds were selectively lithiated at the 4-position in contrast to the corresponding metal free arene compounds. The resulting 4-lithio complexes were converted to the 4-substituted arene compounds in moderate to excellent yields through the reactions with proper electrophiles and subsequent demetalation.     

Dynamics of Decision Making in Animal Group Motion

We analyze a continuous-time model of a multi-agent system motivated by simulation studies on dynamics of decision making in animal groups in motion. Each individual moves at constant speed in the plane and adjusts its heading in response to relative headings of others in the population. The population includes two subgroups that are “informed” such that individuals in each subgroup have a preferred direction of motion. The model exhibits fast and slow time scales allowing for a reduction in the dimension of the problem. The stable solutions for the reduced model correspond to compromise by individuals with conflicting preferences. We study the global phase space for the proposed reduced model by computing equilibria and exploring stability and bifurcations. B. Nabet’s and N.E. Leonard’s work is supported in part by AFOSR grant FA9550-07-1-0-0528 and ONR grants N00014-02-1-0826 and N00014-04-1-0534. I.D. Couzin’s work was supported by the Royal Society, Balliol College and EPSRC grants GR/S04765/01 and GR/T11234/01, a Searle Scholar Award and DARPA grant HR001-05-1-0057. S.A. Levin’s work was supported in part by DARPA grant HR0011-05-1-0057 and NSF grant EF-0434319.     

Determining Hilbert modular forms by central values of Rankin–Selberg convolutions: the weight aspect

The purpose of this paper is to prove that a primitive Hilbert cusp form \(\mathbf{g}\) is uniquely determined by the central values of the Rankin–Selberg L-functions \(L(\mathbf{f}\otimes \mathbf{g}, \frac{1}{2})\), where \(\mathbf{f}\) runs through all primitive Hilbert cusp forms of weight \(k\) for infinitely many weight vectors \(k\). This result is a generalization of the work of Ganguly et al. (Math Ann 345:843–857, 2009) to the setting of totally real number fields, and it is a weight aspect analogue of our previous work (Hamieh and Tanabe in Trans Am Math Soc, arXiv:1609.07209, 2016).     

Gold nanoshell bioconjugates for molecular imaging in living cells

Advances in scattering-based optical imaging technologies offer a new approach to noninvasive point-of-care detection, diagnosis, and monitoring of cancer. Emerging photonics technologies provide a cost-effective means to image tissue in vivo with high resolution in real time. Advancing the clinical potential of these imaging strategies requires the development of optical contrast agents targeted to specific molecular signatures of disease. We describe the use of a novel class of contrast agents based on nanoshell bioconjugates for molecular imaging in living cells. Nanoshells offer significant advantages over conventional imaging probes including continuous and broad wavelength tunability, far greater scattering and absorption coefficients, increased chemical stability, and improved biocompatibility. We show that nanoshell bioconjugates can be used to effectively target and image human epidermal growth factor receptor 2 (HER2), a clinically relevant biomarker, in live human breast carcinoma cells.     

Origin of the X‐ray magnetic circular dichroism at the L‐edges of the rare‐earths in RxR1−x′Al2 systems

An X‐ray magnetic circular dichroism (XMCD) study performed at the rare‐earth L_2,3‐edges in the R_xR_1?x′Al₂ compounds is presented. It is shown that both R and R′ atoms contribute to the XMCD recorded at the L‐edges of the selected rare‐earth, either R or R′. The amplitude of the XMCD signal is not directly correlated to the magnetization or to the value of the individual (R, R′) magnetic moments, but it is related to the molecular field acting on the rare‐earth tuned in the photoabsorption process. This result closes a longstanding study of the origin of the XMCD at the L‐edge of the rare‐earths in multi‐component systems, allowing a full understanding of the exact nature of these signals.     

Sc2C2@C80 rather than Sc2@C82: templated formation of unexpected C2v(5)-C80 and temperature-dependent dynamic motion of internal Sc2C2 cluster

Unambiguous X-ray crystallographic results of the carbene adduct of Sc(2)C(82) reveal a new carbide cluster metallofullerene with the unexpected C(2v)(5)-C(80) cage, that is, Sc(2)C(2)@C(2v)(5)-C(80). More interestingly, DFT calculations and NMR results disclose that the dynamic motion of the internal Sc(2)C(2) cluster depends strongly on temperature. At 293 K, the cluster is fixed inside the cage with two nonequivalent Sc atoms on the mirror plane, thereby leading to C(s) symmetry of the whole molecule. However, when the temperature increases to 413 K, the (13)C and (45)Sc NMR spectra show that the cluster rotates rapidly inside the C(2v)(5)-C(80) cage, featuring two equivalent Sc atoms and weaker metal-cage interactions.