Influence of Amide Connectivity on the Hydrogen-Bond-Directed Self-Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a ≈30-fold increase in the elongation constant for the [2.2]pCp -4,7,12,15-tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp -4,7,12,15-tetracarboxamide ( [2.2]pCpTA ), and a ≈300-fold increase in the elongation constant for the [3.3]pCp -5,8,14,17-tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp -5,8,14,17-tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X-ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π-surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H-bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).     

International Intercomparison of Solar UVR Spectral Measurement Systems in Melbourne in 2013

Monitoring ambient solar UVR levels provides information on how much there is in both real time and historically. Quality assurance of ambient measurements of solar UVR is critical to ensuring accuracy and stability and this can be achieved by regular intercomparisons of spectral measurement systems with those of other organizations. In October and November of 2013 a solar UVR spectroradiometer from Public Health England (PHE) was brought to Melbourne for a campaign of intercomparisons with a new Bentham spectrometer of Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) and one at the Australian Bureau of Meteorology (BOM), supported by New Zealand's National Institute for Water and Atmosphere (NIWA). Given all three spectroradiometers have calibrations that are traceable to various national standards, the intercomparison provides a chance to determine measurement uncertainties and traceability that support UV measurement networks in Australia, New Zealand and the UK. UV Index measurements from all three systems were compared and ratios determined for clear sky conditions when the scans from each instrument were within 2 min of each other. While wavelengths below 305 nm showed substantial differences between the PHE unit and the two other systems, overall the intercomparison results were encouraging, with mean differences in measured UV Index between the BOM/NIWA and those of PHE and ARPANSA of <0.1% and 7.5%, respectively.     

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All‐Organic Redox Flow Battery

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all‐organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical‐based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries.     

Ultraviolet Absorption Induces Hydrogen‐Atom Transfer in G⋅C Watson–Crick DNA Base Pairs in Solution

Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron‐driven proton transfer (EDPT) in Watson–Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine–cytosine (G?C) Watson–Crick base pairs by ultrafast time‐resolved UV/visible and mid‐infrared spectroscopy. The formation of an intermediate biradical species (G[?H]?C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G?C Watson–Crick pairs, but up to 10 % of the initially excited molecules instead form a stable photoproduct G*?C* that has undergone double hydrogen‐atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA.     

Ionic effects on the behavior of thermoresponsive PEO–PNIPAAm block copolymers

The temperature‐dependent aggregation and recovery of the copolymer poly(ethylene oxide)₂₂‐b‐poly(N‐isopropylacrylamide)₂₉ with a C₁₂ end‐cap in aqueous solutions of salts and acids are investigated. Salt solutions affected the critical aggregation temperature of the copolymer in a manner predictable according to the Hofmeister series, with the kosmotropic adipic ion lowering the critical aggregation temperature and the chaotropic iodide raising it. Also, both salts and acids increased the size of copolymer aggregates formed with heating, due to the electrostatic shielding of aggregated structures provided by the electrolytes. Additionally, the presence of ionic additives caused a thermohysteretic increase in the size of copolymer aggregates with temperature cycling. The transitions of polymer structure with increasing temperature were surprisingly sharp with the C₁₂ end‐cap present, and particularly broad in samples in which the end cap had been cleaved. This observation suggested that the hydrophobic end group was responsible for imparting some degree of order to the polymer at low temperatures, which allowed for rapid reconfiguration with increasing temperature. Finally, in addition to the transitions expected from the least critical solution temperature behavior of the polymer blocks, we have observed an unexpected additional transition which we attribute to the contraction of the poly(ethylene oxide) chains of the copolymer aggregates at higher temperatures. This work illustrates the importance of considering the environment and composition of thermoresponsive block copolymers in certain applications, particularly in solutions with even modest electrolyte concentrations (1–10 mM), as it can have a profound effect on transition temperatures and morphology. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 507–516     

β-Ketoiminato Iridium(III) Organometallic Complexes: Selective Cytotoxicity towards Colorectal Cancer Cells HCT116 p53-/-

This report presents a new library of organometallic iridium(III) compounds of the type [Cp*IrCl(L)] (Cp*=pentamethylcyclopentadienyl and L=a functionalized β-ketoiminato ligand) showing moderate to high cytotoxicity against a range of cancer cell lines. All compounds show increased activity towards colorectal cancer, with preferential activity observed against the immortalized p53-null colorectal cell line, HCT116 p53-/-, with sensitivity factors (SF) up to 26.7. Additionally, the compounds have excellent selectivity for cancerous cells when tested against normal cell types, with selectivity ratios (SR) up to 35.6, contrary to that of cisplatin, which is neither selective nor specific for cancerous cells (SF=0.43 and SR=0.7–2.3). This work provides a preliminary understanding of the cytotoxicity of iridium compounds in the absence of p53 and has potential applications in treatment of cancers for which the p53 gene is absent or mutant.     

Liquid-vapour coexistence and correlations in the interface

From the derivative of the statistical mechanical definition of the number density (the first Yvon equation), we derive an infinite set of sum rules that must be satisfied by the density profile and the pair correlation function of a liquid-vapour system with pairwise central interactions. For a particular class of approximate pair correlation functions, the sum rules reduce to equations linking the pressure and temperature with the densities of the two bulk phases. Good agreement with experimental data is obtained.