Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.     

A Noninvasive, on Wafer Method to Determine the Intrinsic Stress of a Polymer Layer

The method described in this paper allows an investigator to determine the intrinsic stress of a polymer layer in a way that does not result in damage to devices or test structures. The method requires that a small area of the polymer be released from the substrate to form a diaphragm. The diaphragm is stimulated with acoustic white noise and the diaphragm movement is monitored with a laser vibrometer. The first few resonance frequencies of the diaphragm are obtained using a laser vibrometer and then those frequencies are used to calculate the membrane intrinsic bi-axial tension.     

Counting unrooted maps on the plane

A planar map is a 2-cell embedding of a connected planar graph, loops and parallel edges allowed, on the sphere. A plane map is a planar map with a distinguished outside (“infinite”) face. An unrooted map is an equivalence class of maps under orientation-preserving homeomorphism, and a rooted map is a map with a distinguished oriented edge. Previously we obtained formulae for the number of unrooted planar n-edge maps of various classes, including all maps, non-separable maps, eulerian maps and loopless maps. In this article, using the same technique we obtain closed formulae for counting unrooted plane maps of all these classes and their duals. The corresponding formulae for rooted maps are known to be all sum-free; the formulae that we obtain for unrooted maps contain only a sum over the divisors of n. We count also unrooted two-vertex plane maps.     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Quantitative Impact of a Cognitive Modeling Intelligent Tutoring System on Student Performance in Balancing Chemical Equations

The need for improved interactive tutoring capabilities in educational software for chemistry problem solving is an important one clearly articulated by teachers and students. To deliver the next generation of individualized interactive capabilities users demand, it is necessary to go beyond the conventional computer-assisted instruction methodology. The focus of this paper is the assessment with first-semester general chemistry students of a recently developed artificial intelligence (AI) tutor for balancing chemical equations. This is the first such assessment of an AI-based learning tool in chemistry. Students in CHEM 121 in the Fall 2001 semester at Duquesne University (N = 273) participated in the study. Students were divided into a test group that used the AI tutor as part of their study activities and a control group that did not use the tutor. It was found that the tutor improved the performance of the test group students to a statistically significant degree, helping the weakest students the most. This study establishes the feasibility of an AI-based approach to creating advanced new tutoring software for chemistry problem solving. Access to a Web-based demonstration of the equation-balancing tutor may be obtained by emailing the corresponding author.     

Non-trivial simple poles at negative integers and mass concentration at singularity

Let (X,0) be the germ of a normal space of dimension n+1 and let f be the germ at 0 of a holomorphic function on X. Assume both X and f have an isolated singularity at 0. Denote by J the image of the restriction map , where F is the Milnor fibre of f at 0. We prove that the canonical Hermitian form on , given by poles of order at in the meromorphic extension of , passes to the quotient by J and is non-degenerate on . We show that any non-zero element in J produces a “mass concentration” at the singularity which is related to a simple pole concentrated at for (in a non-na?ve sense). We conclude with an application to the asymptotic expansion of oscillatory integrals , for , when . Received: 28 May 2001 / Published online: 26 April 2002     

Equilibrium studies of Mn(II), Mg(II), Ca(II), Sr(II) and Ba(II) withp-fluoro-,p-chloro-,p-bromo-,p-methyl-benzoylacetones and 1-(4-fluorophenyl)-1,3-pentanedione

The rawpH-data, obtained from the potentiometric titrations of the titled ligands with NaOH in 75% (v/v) dioxane-water mixture performed at 20, 30 and 40°C at constant ionic strength (=0.1M-NaClO₄), have been adequately corrected for dilution, and solvent effects in order to evaluate thermodynamic dissociation constants. Variance of the latter as a function of temperature has also been accounted for. The differing magnitudes of thermodynamic dissociation constants of the titled ligands have been explained on the basis of the non coplanar orientation of the phenyl ring in the ligands and a comparison has been made with those of unsubstituted benzoylacetone, dibenzoylmethane and acetylacetone.Following similar technique, thermodynamic stepwise and overall formation constants of the titled metal-ligand systems have been obtained and the results correlated with ligand basicity inverse metal crystal radii and second potentials of metals. Decrease in the free enthalpy (–G) of complexation reaction has also been evaluated.

---

Untersuchung der Gleichgewichte von Mn(II), Mg(II), Ca(II), Sr(II) und Ba(II) mit p-Fluor-, p.-Chlor-, p-Brom-, p-Methyl-benzoylaceton und 1-(4-Fluorphenyl)-1,3-pentanedion

Zusammenfassung Aus der potenitometrischen Titration der Titelverbindungen mit NaOH in 75 (v/v) Dioxan—Wasser bei, 20, 30 und 40°C bei konstanter Ionenstärke (=0,1M-NaClO₄) wurden die thermodynamischen Dissoziationskonstanten ermittelt. Verdünnungs-, Lösungsmittel-und Temperatureffekte wurden berücksichtigt. Die unterschiedlichen Dissoziationskonstanten werden mit der Nichtplanarität des Phenylrings in den Liganden erklärt. Außerdem wurden die Komplexbildungskonstanten bestimmt; sie sind in die Diskussion miteinbezogen.

     

Colloidal nano-MOFs nucleate and stabilize ultra-small quantum dots of lead bromide perovskites

The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr₃O(OH)(H₂O)₂(terephthalate)₃ (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr₃, MAPbBr₃ (MA⁺ = methylammonium), and (FA)PbBr₃ (FA⁺ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr₃ (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.

We demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites.     

Etude dans la serie des organosilylazoles : I. Action des halogenures d'alkyle,des chlorures d'acide et des cetones halogenees

The reactivity of organosilylamines of imidazole, pyrazole, 1,2,4-triazole and benzotriazole towards alkyl halides, acidic chlorides and halogenated ketones has been studied. Except for 1-trimethylsilylimidazole, which gives a mixed quaternary salt, reactions with primary halides lead to the corresponding 1-alkylated heterocyclic compounds in high yields; in each case only one isomer is obtained (1-alkyl-1,2,4-triazole and 1-alkylbenzotriazole). Similarly acidic chlorides give 1-acylated derivatives in quantitative yields. Finally α- or β-halogenated ketones show different behaviour and give the addition or substitution products.