Pfeiffer effect on configurationally labile dyes within ternary complexes with metal ions and enantiopure macrocycles.

A configurationally-labile helical dye, 2,4,5,7-tetranitrofluorenone oximate, is used to probe complexes made of enantiopure macrocycles and mono/divalent metal ions. Induced electronic circular dichroism (ECD) and 1H NMR responses are amplified at room temperature only in the presence of K+ and Na+ ions despite larger binding efficiency with alkaline earth metal ions.

Sulfate-induced large amplitude conformational change in a Solomon link.

A doubly-interlocked [2]catenane - or Solomon link - undergoes a complex conformational change upon addition of sulfate in methanol. This transformation generates a single pocket where two SO42- anions bind through multiple hydrogen bonds and electrostatic interactions. Despite the close proximity of the two anions, binding is highly cooperative.

2,4,5,7-Tetranitrofluorenone Oximate for the Naked-Eye Detection of H-Bond Donors and the Chiroptical Sensing of Enantiopure Reagents.

Hydrogen bonding greatly influences rates and equilibrium positions of chemical reactions, conformations, and sometimes even stereochemistry. This study reports on tetranitrofluorenone oximate, a novel dye capable of naked-eye detection of hydrogen-bond donating species (HBDs) and of rapid determination of H-bond donation strength by hypsochromic shift monitoring. In addition, the molecule possesses atropisomeric conformations, of M and P configuration, as evidenced in solid and solution state studies by X-ray diffraction and electronic circular dichroism (ECD), respectively. In the latter case, enantiopure bis-thioureas were the most effective HBDs to promote a chiral induction (diastereoselective recognition, Pfeiffer effect); the ECD results being rationalized by time-dependent density functional theory (TDDFT) calculations. Based on these experiments, bis-thioureas were used as chiral reagents in asymmetric 1,3-dipolar cycloadditions of structurally-related nitrones; the ECD sensing of the stereoinduction between bis-thioureas and the oximate serving as an indirect method of selection of the most effective HBD for asymmetric synthesis.

Diastereoselective Amplification of a Mechanically Chiral [2]Catenane.

Achiral [2]catenanes composed of rings with inequivalent sides may adopt chiral co-conformations. Their stereochemistry depends on the relative orientation of the interlocked rings and can be controlled by sterics or an external stimulus (e.g., a chemical stimulus). Herein, we have exploited this stereodynamic property to amplify a mechanically chiral (P)-catenane upon binding to (R)-1,1'-binaphthyl 2,2'-disulfonate, with a diastereomeric excess of 85%. The chirality of the [2]catenane was ascertained in the solid state by single crystal X-ray diffraction and in solution by NMR and CD spectroscopies. This study establishes a robust basis for the development of a new synthetic approach to access enantioenriched mechanically chiral [2]catenanes.

Simultaneous measurements of dissolved CH4 and H2 in wetland soils.

Biogeochemical processes in wetland soils are complex and are driven by a microbiological community that competes for resources and affects the soil chemistry. Depending on the availability of various electron acceptors, the high carbon input to wetland soils can make them important sources of methane production and emissions. There are two significant pathways for methanogenesis: acetoclastic and hydrogenotrophic methanogenesis. The hydrogenotrophic pathway is dependent on the availability of dissolved hydrogen gas (H2), and there is significant competition for available H2. This study presents simultaneous measurements of dissolved methane and H2 over a 2-year period at three tidal marshes in the New Jersey Meadowlands. Methane reservoirs show a significant correlation with dissolved organic carbon, temperature, and methane emissions, whereas the H2 concentrations measured with dialysis samplers do not show significant relationships with these field variables. Data presented in this study show that increased dissolved H2 reservoirs in wetland soils correlate with decreased methane reservoirs, which is consistent with studies that have shown that elevated levels of H2 inhibit methane production by inhibiting propionate fermentation, resulting in less acetate production and hence decreasing the contribution of acetoclastic methanogenesis to the overall production of methane.

Synthesis and Enantiomeric Recognition Studies of Optically Active Pyridino-Crown Ethers Containing an Anthracene Fluorophore Unit.

Novel enantiopure pyridino-18-crown-6 ether-based sensor molecules containing an anthracene fluorophore unit were synthesized. Their enantiomeric recognition abilities toward the enantiomers of 1-phenylethylamine hydrogen perchlorate (PhEt), 1-(1-naphthyl)ethylamine hydrogen perchlorate (NapEt), phenylglycine methyl ester hydrogen perchlorate (PhgOMe), and phenylalanine methyl ester hydrogen perchlorate (PheOMe) were examined in acetonitrile using fluorescence spectroscopy. The sensor molecules showed appreciable enantiomeric recognition toward the enantiomers of NapEt, PhEt, and PhgOMe. The highest enantioselectivity was found in the case of crown ether containing isobutyl groups in the macroring and the enantiomers of NapEt. Chirality 28:562-568, 2016. © 2016 Wiley Periodicals, Inc.

Albumin nanoshell encapsulation of near-infrared-excitable rare-Earth nanoparticles enhances biocompatibility and enables targeted cell imaging.

The use of traditional fluorophores for in vivo imaging applications is limited by poor quantum yield, poor tissue penetration of the excitation light, and excessive tissue autofluorescence, while the use of inorganic fluorescent particles that offer a high quantum yield is frequently limited due to particle toxicity. Rare-earth-doped nanoparticles that utilize near-infrared upconversion overcome the optical limitations of traditional fluorophores, but are not typically suitable for biological application due to their insolubility in aqueous solution, lack of functional surface groups for conjugation of biomolecules, and potential cytotoxicity. A new approach to establish highly biocompatible and biologically targetable nanoshell complexes of luminescent rare-earth-doped NaYF(4) nanoparticles (REs) excitable with 920-980 nm near-infrared light for biomedical imaging applications is reported. The approach involves the encapsulation of NaYF(4) nanoparticles doped with Yb and Er within human serum albumin nanoshells to create water-dispersible, biologically functionalizable composite particles. These particles exhibit narrow size distributions around 200 nm and are stable in aqueous solution for over 4 weeks. The albumin shell confers cytoprotection and significantly enhances the biocompatibility of REs even at concentrations above 200 microg REs mL(-1). Composite particles conjugated with cyclic arginine-glycine-aspartic acid (cRGD) specifically target both human glioblastoma cell lines and melanoma cells expressing alpha(v)beta(3) integrin receptors. These findings highlight the promise of albumin-encapsulated rare-earth nanoparticles for imaging cancer cells in vitro and the potential for targeted imaging of disease sites in vivo.