Effects of pi-bonding on stability and reactivity in

Recent synthetic and theoretical investigations of organometallic compounds containing the CpCr(NO) fragment have shown an interdependence of the electronic nature of ancillary ligands and the stability of a given Cr oxidation state. Understanding the correlation between ligand pi-bonding properties and the nature of the metal-based frontier orbitals permits the rationalization of observed reactivity patterns, and the identification and preparation of new classes of target molecules.     

Dropwise Condensation of Steam on a Small Tube Bundle at Turbine Condenser Conditions

Application of dropwise condensation to utility turbine condensers is investigated by comparing the thermal performance of dropwise and filmwise bundles at industrially relevant conditions. Steam and steam-air mixtures were condensed on bundles of in-line, titanium tubes. The row-by-row heat transfer coefficients are presented against bundle position. They show the expected behavior for filmwise condensation but demonstrate a different one for dropwise. In air-free steam, the dropwise heat transfer coefficients are much larger and do not vary significantly with bundle position. In air-steam mixtures the dropwise values decrease similarly to their filmwise equivalents. The findings are in accord with those found for other geometries. The findings indicate that significant reductions in condenser size can be obtained if permanent dropwise condensation can be produced at industrially relevant conditions.     

Reactive ligand influence on initiation in phenylene catalyst‐transfer polymerization

Synthesizing conjugated polymers via catalyst‐transfer polymerization (CTP) has led to unprecedented control over polymer sequence and molecular weight. Yet many challenges remain, including broadening the monomer scope and narrowing the molecular weight dispersities. Broad polymer dispersities can arise from nonliving pathways as well as slow initiation. Previously, slow initiation was observed in Ni‐mediated CTP of phenylene monomers. Although precatalysts with faster initiation rates have been reported, the rates still do not exceed propagation. Herein a second‐ and third‐generation of reactive ligands are described, along with a simple method for measuring initiation rates. A precatalyst with an initiation rate that exceeds propagation is now reported, however, the resulting polymer samples still exhibit broad dispersities, suggesting that slow initiation is not the most significant contributing factor in Ni‐mediated phenylene polymerizations. In addition, initiation rates measured under authentic polymerization conditions revealed that both exogenous triphenylphosphine and an ortho‐trifluoroethoxy substituent on the reactive ligand have a strong influence. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1530–1535     

Four-wave mixing with self-phase matching due to collective atomic recoil

We describe a method for nondegenerate four-wave-mixing in a cold sample of four-level atoms. An integral part of the four-wave-mixing process is a collective instability which spontaneously generates a periodic density modulation in the cold atomic sample with a period equal to half of the wavelength of the generated high-frequency optical field. Because of the generation of this density modulation, phase matching between the pump and scattered fields is not a necessary initial condition for this wave-mixing process to occur; rather the density modulation acts to "self-phase match" the fields during the course of the wave-mixing process. We describe a one-dimensional model of this process, and suggest a proof-of-principle experiment which would involve pumping a sample of cold Cs atoms with three infrared pump fields to produce blue light.     

Toward biodegradable nanogel star polymers via organocatalytic ROP

Organocatalytic ring opening polymerization (OROP) is used to effect the rapid, scalable, room temperature formation of size-controlled, highly uniform, polyvalent, nanogel star polymer nanoparticles of biodegradable composition.     

From Archimedean to Liouville copulas

We use a recent characterization of the d-dimensional Archimedean copulas as the survival copulas of d-dimensional simplex distributions (McNeil and Nešlehová (2009) [1]) to construct new Archimedean copula families, and to examine the relationship between their dependence properties and the radial parts of the corresponding simplex distributions. In particular, a new formula for Kendall’s tau is derived and a new dependence ordering for non-negative random variables is introduced which generalises the Laplace transform order. We then generalise the Archimedean copulas to obtain Liouville copulas, which are the survival copulas of Liouville distributions and which are non-exchangeable in general. We derive a formula for Kendall’s tau of Liouville copulas in terms of the radial parts of the corresponding Liouville distributions.