Hydrogen bond formation to cyclic and acyclic polyethers

Equilibrium constants and enthalpies of hydrogen-bond formation of mcresol to various cyclic (crown) and acyclic polyethers have been determined in benzene solvent. Equilibrium constants indicated no evidence for an operative macrocyclic effect; the relationship between the increasing size of the equilibrium constant and the number of ether oxygens was rationalized with a simple statistical thermodynamic model. Enthalpies of interactions ranged between –19 and –23 kJ-mol^–1. In agreement with PCILO calculations, enthalpies of interaction were essentially independent of the number of oxygen atoms in the ether; no significant difference in enthalpies of interaction between cyclic and acyclic ethers was found.     

Liquid chromatographic determination of 4,4'-dinitrocarbanilide, the active component of the infertility agent nicarbazin, in chicken, duck, goose, and snake eggs

4,4'-Dinitrocarbanilide (DNC) was extracted from chicken, duck, goose, and snake eggs and isolated by reversed-phase liquid chromatography. DNC was detected by ultraviolet absorbance at 347 nm and quantitated by comparison with a calibration standard. Recoveries of DNC from fortified control chicken, duck, goose, and snake egg samples were determined for DNC levels of 0.16, 10, and 16 microg/g. The mean recoveries from chicken, duck, goose, and snake eggs were 92 +/- 4, 88 +/- 9, 87 +/- 7, and 95 +/- 6%, respectively. The method limits of detection for DNC in chicken, duck, goose, and snake eggs ranged from 0.015 to 0.035 microg/g. The reported method is much simpler than and equally efficient as previous methods developed for the determination of DNC residues in egg contents.     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Colloidal Nanocrystals of Lithiated Group 14 Elements

The synthesis of colloidal nanocrystals (NCs) of lithiated group 14 elements (Z=Si, Ge, and Sn) is reported, which are Li_4.4Si, Li_3.75Si, Li_4.4Ge, and Li_4.4Sn. Li_xZ compounds are highly reactive and cannot be synthesized by existing methods. The success relied on separating the surface protection from the crystal formation and using a unique passivating ligand. Bare Li_xZ crystals were first produced by milling elemental Li and Z in an argon‐filled jar. Then, under the assistance of additional milling, hexyllithium was added to passivate the freshly generated Li_xZ NCs. This ball‐milling‐assisted surface protection method may be generalized to similar systems, such as Na_xZ and K_xZ. Moreover, Li_4.4Si and Li_4.4Ge NCs were conformally encapsulated in carbon fibers, providing great opportunities for studying the potential of using Li_xZ to mitigate the volume‐fluctuation‐induced poor cyclability problem confronted by Z anodes in lithium‐ion batteries.     

1H, 13C, and 73Ge NMR spectral analysis of substituted aryltrimethylgermanes

NMR chemical shifts of 1H, 13C, and 73Ge are reported for a series of monosubstituted aromatic trimethylgermanes of the type XC6H4Ge(CH3)3; X = p-N(CH3)2, p-OCH3, p-OC2H5, p-C(CH3)3, p-Si(CH3)3, p-Ge(CH3)3, p-Sn(CH3)3, p-CH3, m-CH3, -H, m-OCH3, p-Cl, p-Br, m-F, m-CF3, p-CF3, o-OCH3, and o-CH3. The relatively narrow 73Ge resonances show a strong correlation with Hammett sigma constants, with a correlation coefficient of 0.976 and 0.876 for 73Ge chemical shifts in meta- and para-substituted derivatives, respectively. The 13C chemical shifts of the methyl carbons bonded to germanium also display a relationship, with correlation coefficients of 0.904, 0.993, and 0.911 for para-, meta- and all derivatives, respectively. Comparisons of the Hammett plots for the homologous series XC6H4M(CH3)3; M = C, Si, Ge, Sn, show that, in general, correlation coefficients decrease while slopes increase significantly down the group, presumably reflecting the corresponding increase in chemical shift range of the group 14 atom. The Hammett constant derived for the p-Ge(CH3)3 group of +0.13 compares with the NMR-derived constants of -0.12 for p-C(CH3)3, +0.14 for p-Si(CH3)3, and -0.14 for p-Sn(CH3)3. The indication of electron release by carbon and tin can be rationalized through traditional hyperconjugative arguments for carbon and by the low electronegativity and consequent inductive effect of tin. The small electron attraction suggested by the positive constants for silicon and germanium can be simply, and perhaps naively, attributed to pi-acceptor interactions with the benzene ring.     

Chiral proton catalysis: a catalytic enantioselective direct aza-Henry reaction

Despite Nature's longstanding ability to use a proton, the most prevalent Lewis acid, to both activate and orient a substrate during an enantioselective reaction, this work represents the first example of this phenomenon outside of a protein. A chiral, nonracemic BisAMidine (BAM) ligand was designed, synthesized, and complexed to the proton of a Br?nsted acid. The resulting coordination compound catalyzed the production of enantioenriched product from the combination of a Schiff base and nitroalkane (the aza-Henry reaction). This particular reaction is also considered a model for many analogous carbon-carbon bond-forming reactions catalyzed by enzymes (e.g., the Mannich reaction). This discovery suggests the use of ionic hydrogen bonds in asymmetric catalysis may not only be more general than previously thought, but also a viable "green" approach to single-enantiomer organic compounds.     

Eine Methode zur Bestimmung der ?pfels?ure

Ohne Zusammenfassung     

Further Development and Validation of the Teaching Science as Inquiry (TSI) Instrument

The purpose of this study was to further develop and validate the Teaching Science as Inquiry (TSI) Instrument, an instrument designed to measure the self‐efficacy beliefs of preservice teachers in regards to the teaching of science as inquiry. Based on the validation processes and the associated data analysis, the TSI demonstrates continued content and construct validity with high internal reliability when used with prospective elementary science teachers.     

High temperature arc studies of infrared radiation from boron and tungsten oxides

Long wavelength infrared emission spectra from boron and tungsten compounds in air were obtained in a d.c. arc jet at 3000–6000°K for the wavelength range 1·2–24 μm. Absolute vibrational band intensities were measured for WO, WO₂, WO₃, BO, BOF and BF₃ molecules. Several unidentified bands were observed and are discussed.