ON THE PHOSPHORUS-31 CHEMICAL SHIFTS OF SUBSTITUTED TRIARYLPHOSPHINES

Abstract

The ³¹P chemical shifts of eleven (4-ZC₆H₄)₃P compounds show a slight correlation with the Hammet [sgrave]para constant of Z. The unusually large upfield chemical shifts of (2-ZC₆H₄)₃P compounds are attributed to an extreme “gamma” effect caused by the restricted conformations due to the steric influence of the ortho substituents. Chemical shifts are given for about thirty triarylphosphines, and group contributions to phosphine chemical shifts are listed for twenty-one aryl groups.     

Crystallization of Pseudopolymorphs of Some Gamboge Pigments. Pyridine,Dimethylformamide and Dimethylsulfoxide Solvates of Morellic Acid,Gambogic Acid and Guttiferic Acid

Abstract

Morellic acid, gambogic acid and guttiferic acid are related naturally-occurring xanthone pigments that yield X-ray quality crystals only from solvents like pyridine, dimethylformamide (dmf) and dimethyl sulfoxide (dmso). The structures of four of these crystals have been determined and are found to contain solvents of crystallization. The solvents hydrogen bond to the carboxyl groups with O—H…O/N motifs previously seen in other carboxylic acids. Distinctive, however, is the presence of an extended though somewhat diffuse array of C—H…O hydrogen bonds that aggregates the entire solute-solvent assemblage in a multi-point manner. Pyridine and dmf are able to mimic each other with respect to their hydrogen bond donating and accepting characteristics and in this respect play equivalent roles in their solvates with morellic acid and gambogic acid. Dmso is seen to self-associate in its guttiferic acid solvate. It is possible that these solvents with multiple hydrogen bonding donor and acceptor capability can act as hydrogen bond nucleators, providing just enough rigidity to the solutes to ensure crystallization.     

Quantum nonlocality and beyond: limits from nonlocal computation

We address the problem of "nonlocal computation," in which separated parties must compute a function without any individual learning anything about the inputs. Surprisingly, entanglement provides no benefit over local classical strategies for such tasks, yet stronger nonlocal correlations allow perfect success. This provides intriguing insights into the limits of quantum information processing, the nature of quantum nonlocality, and the differences between quantum and stronger-than-quantum nonlocal correlations.     

Bioorthogonal Turn-On BODIPY-Peptide Photosensitizers for Tailored Photodynamic Therapy

Photodynamic therapy (PDT) leads to cancer remission via the production of cytotoxic species under photosensitizer (PS) irradiation. However, concomitant damage and dark toxicity can both hinder its use. With this in mind, we have implemented a versatile peptide-based platform of bioorthogonally activatable BODIPY-tetrazine PSs. Confocal microscopy and phototoxicity studies demonstrated that the incorporation of the PS, as a bifunctional module, into a peptide enabled spatial and conditional control of singlet oxygen (¹O₂) generation. Comparing subcellular distribution, PS confined in the cytoplasmic membrane achieved the highest toxicities (IC₅₀=0.096±0.003 μm ) after activation and without apparent dark toxicity. Our tunable approach will inspire novel probes towards smart PDT.     

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

The solution‐phase synthesis is one of the most promising strategies for the preparation of well‐defined graphene nanoribbons (GNRs) in large scale. To prepare high quality, defect‐free GNRs, cycloaromatization reactions need to be very efficient, proceed without side reaction and mild enough to accommodate the presence of various functional groups. In this Minireview, we present the latest synthetic approaches for the synthesis of GNRs and related structures, including alkyne benzannulation, photochemical cyclodehydrohalogenation, Mallory and Pd‐ and Ni‐catalyzed reactions.     

Complexes of tricoordinate hypervalent pnictogens with pentamethylcyclopentadienylruthenium

The complexes of a pentamethylcyclopentadienylruthenium moiety with hypervalent tricoordinate pnictogens are reported. A unique mode of complexation is observed for each of the different pnictogens (P, As, Sb). The phosphorus derived complex exhibits an 8-electron tetrahedral bonding environment at phosphorus. The antimony derived complex maintains a 10-electron bonding system at antimony with a pseudo-trigonalbipyramidal geometry at antimony. The arsenic-containing complex is formed with destruction of the original arsenic heterocycle and formation of a trinuclear Ru–Ru–As ring. Remarkably, the formation of the arsenic ruthenium complex can be reversed to reconstruct the original arsenic heterocycle.     

A Mechanism of High-Tc Superconductivity Relating to Perovskite Crystal Structure

A mechanism of high-T_c superconductivity related to the perovskite crystal structure is proposed by a “phonon attenuation model”, which means that in the perovskite-like crystal structure, a number of “ordering” vacancies or holes occur due to the non-stoichiometric structure features. Such a reticular “spongly-like” structure facilitates lattice thermovibration attenuation perovskite (phonon attenuation) during temperature reduction. This leads to an abrupt drop of the resistivity, owing to the conduction electrons transmitted through the media without collision with irregularities in the lattice due to the lattice thermovibration. This probably is the main reason for high-T_c superconductivity of the perovskite cuprates.