Alcohols as Fluoroalkyl Synthons: Ni-catalyzed Dehydrogenative Approach to Access Polyfluoroalkyl Bis-indoles

An acceptorless dehydrogenative strategy for the synthesis of polyfluoroalkylated bis-indoles is described by employing an earth-abundant nickel-based catalytic system under air. The notable feature of the present transformation is the use of bench stable and easily affordable polyfluorinated alcohols without any pre-functionalization for the introduction of precious polyfluoroalkyl groups. The developed straightforward protocol accomplished biologically relevant fluoroalkyl bis-indoles in a sustainable fashion. Extensive DFT study predicts the unique role of indole molecules which stabilizes the transition states during the dehydrogenation process of polyfluorinated alcohols, presumably through non-covalent π⋅⋅⋅π and H-bonding interactions.     

Induced Production,Synthesis, and Immunomodulatory Action of Clostrisulfone,a Diarylsulfone from Clostridium acetobutylicum

The anaerobe Clostridium acetobutylicum belongs to the most important industrially used bacteria. Whereas genome mining points to a high potential for secondary metabolism in C. acetobutylicum, the functions of most biosynthetic gene clusters are cryptic. We report that the addition of supra-physiological concentrations of cysteine triggered the formation of a novel natural product, clostrisulfone ( 1 ). Its structure was fully elucidated by NMR, MS and the chemical synthesis of a reference compound. Clostrisulfone is the first reported natural product with a diphenylsulfone scaffold. A biomimetic synthesis suggests that pentamethylchromanol-derived radicals capture sulfur dioxide to form 1 . In a cell-based assay using murine macrophages a biphasic and dose-dependent regulation of the LPS-induced release of nitric oxide was observed in the presence of 1 .     

Effective spectral emissivity measurements of superalloys and YSZ thermal barrier coating at high temperatures using a 1.6μm single wavelength pyrometer

A method which employs an integrating sphere and a single-wavelength (1.6 μm) pyrometer for measuring the spectral effective emissivities of superalloys in the temperature range (=650–1050°C) is described. The spectral effective emissivities for five superalloys, namely, MARM-247, MARM-509, CMSX-4, Inconel-718, N-155 and two René-N6 samples coated with YSZ thermal barrier coating were measured. Correcting the pyrometer measurements for the variations in the object emissivity would reduce the uncertainty in the temperature measurements to <±1%.     

Inverse estimation of indoor airflow patterns using singular value decomposition

The fast pace in the development of indoor sensors and communication technologies is allowing a great amount of sensor data to be utilized in various areas of indoor air applications, such as estimating indoor airflow patterns. The development of such an inverse model and the design of a sensor system to collect appropriate data are discussed in this study. Algebraic approaches, including singular value decomposition (SVD), are evaluated as methods to inversely estimate airflow patterns given limited sensor measurements. In lieu of actual sensor data, computational fluid dynamics data are used to evaluate the accuracy of the airflow patterns estimated by the inverse models developed in this study. It was found that the airflow patterns estimated by the linear inverse SVD model were as accurate as those estimated by the nonlinear inverse-multizone model. For the zones tested, sensor measurements along on the walls and near the inlet and outlet provided the greatest improvement in the accuracy of the estimated airflow patterns when compared with the results using measurements from other locations.     

Valid inequalities for MIPs and group polyhedra from approximate liftings

In this paper, we present an approximate lifting scheme to derive valid inequalities for general mixed integer programs and for the group problem. This scheme uses superadditive functions as the building block of integer and continuous lifting procedures. It yields a simple derivation of new and known families of cuts that correspond to extreme inequalities for group problems. This new approximate lifting approach is constructive and potentially efficient in computation. J.-P. P. Richard was supported by NSF grant DMI-348611.     

Sooting tendencies of nonvolatile aromatic hydrocarbons

We have measured sooting tendencies of 72 nonvolatile aromatic hydrocarbons, only five of which have been previously reported in the literature. The tested compounds include long-chain alkylbenzenes up to tridecylbenzene, methyl-substituted benzenes, naphthalenes, biaryls, and polycyclic aromatic hydrocarbons (PAH) with up to four rings. Sooting tendency was defined as the maximum soot concentration f_v,max in a methane/air coflow nonpremixed flame with 5-80 ppm of the aromatic added to the fuel. The f_v,max were converted into Yield Sooting Indices (YSI’s) by the equation YSI = C^∗f_v,max + D, where C and D are constants chosen so that YSI-2-heptanone = 17 and YSI-phenanthrene = 191. The aromatics were dissolved in 2-heptanone and added to the fuel mixture with a syringe pump. Soot concentrations were measured with laser-induced incandescence (LII). The burner and fuel lines were heated; time-resolved soot measurements verified that all of the test compounds were quantitatively transmitted to the flame without losses to the walls. The uncertainties in the results range from ±3 to ±10%.     

Congruences of multipartition functions modulo powers of primes

Let p _r (n) denote the number of r-component multipartitions of n, and let S _γ,λ be the space spanned by η(24z) ^γ ?(24z), where η(z) is the Dedekind’s eta function and ?(z) is a holomorphic modular form in \(M_{\lambda}(\mathrm{SL}_{2}(\mathbb{Z}))\) . In this paper, we show that the generating function of \(p_{r}(\frac{m^{k} n +r}{24})\) with respect to n is congruent to a function in the space S _γ,λ modulo m ^k . As special cases, this relation leads to many well known congruences including the Ramanujan congruences of p(n) modulo 5,7,11 and Gandhi’s congruences of p ₂(n) modulo 5 and p ₈(n) modulo 11. Furthermore, using the invariance property of S _γ,λ under the Hecke operator \(T_{\ell^{2}}\) , we obtain two classes of congruences pertaining to the m ^k -adic property of p _r (n).     

Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

Since the first heavy alkene analogues of germanium and tin were isolated in 1976, followed by West''s disilene in 1981, the chemistry of stable group 14 dimetallenes and dimetallynes has advanced immensely. Recent developments in this field veered the focus from the isolation of novel bonding motifs to mimicking transition metals in their ability to activate small molecules and perform catalysis. The potential of these homonuclear multiply bonded compounds has been demonstrated numerous times in the activation of H₂, NH₃, CO₂ and other small molecules. Hereby, the strong relationship between structure and reactivity warrants close attention towards rational ligand design. This minireview provides an overview on recent developments in regard to bond activation with group 14 dimetallenes and dimetallynes with the perspective of potential catalytic applications of these compounds.

This minireview highlights the recent advances in small molecule activation and catalytic applications of homonuclear dimetallenes, dimetallynes and interconnected bismetallylenes of heavier group 14 elements.