Thermal racemization of biaryl atropisomers

Many biaryl compounds possess atropisomerism due to the steric hindrance of substituents at the ortho-position of the two aromatic moieties. Upon heating, atropisomers may have enough energy to surpass the rotational energy barrier and racemize. The thermal stability of five atropisomers was studied using chiral chromatography by following the change in enantiomeric excess ratio at different temperatures. The first order racemization reaction rate was obtained at a given temperature as the slope of the change in enantiomeric excess ratio versus time. For each atropisomer, the racemization rates at different temperatures led to the value of the rotational energy barrier for racemization, ΔG³, and to the racemization half lifetime, t_1/2, indicating the atropisomer thermal stability. Binaphthol started to racemize significantly at temperature of 190 °C and above while binaphthyldiamine was much more stable showing little or very minor racemization up to 210 °C. A chloro-substituted phenylamino-naphthol was very sensitive to thermal racemization starting at a low 40 °C.     

SYNTHESIS, CHARACTERIZATION OF DIAMIDE-DIIMIDE-DIAMINES BASED ON L-CYSTEINE AMINO ACID AND THEIR EFFECT ON THE THERMAL PROPERTIES OF DIGLYCIDYL ETHER OF BISPHENOL-A (DGEBA)

The curing behavior of diglycidyl ether of bisphenol-A(DGEBA) with aromatic diamide-diimide-diamines having aryl ether,sulfone and methylene linkages was studied by differential scanning calorimetry(DSC).Nine diamide-diimide-diamines of varying structure were synthesized by reacting 1 mole of dianhydride with 2 moles of L-cysteine(S) in a mixture of acetic acid and pyridine(3:2 V/V) followed by activation with thionyl chloride(SOCl_2) and then condensation with excess of diamines.Structural characterizat...     

On the chemical kinetics of n-butanol: ignition and speciation studies

Direct measurements of intermediates of ignition are challenging experimental objectives, yet such measurements are critical for understanding fuel decomposition and oxidation pathways. This work presents experimental results, obtained using the University of Michigan Rapid Compression Facility, of ignition delay times and intermediates formed during the ignition of n-butanol. Ignition delay times for stoichiometric n-butanol/O(2) mixtures with an inert/O(2) ratio of 5.64 were measured over a temperature range of 920-1040 K and a pressure range of 2.86-3.35 atm and were compared to those predicted by the recent reaction mechanism developed by Black et al. (Combust. Flame 2010, 157, 363-373). There is excellent agreement between the experimental results and model predictions for ignition delay time, within 20% over the entire temperature range tested. Further, high-speed gas sampling and gas chromatography techniques were used to acquire and analyze gas samples of intermediate species during the ignition delay of stoichiometric n-butanol/O(2) (χ(n-but) = 0.025, χ(O(2)) = 0.147, χ(N(2)) = 0.541, χ(Ar) = 0.288) mixtures at P = 3.25 atm and T = 975 K. Quantitative measurements of mole fraction time histories of methane, carbon monoxide, ethene, propene, acetaldehyde, n-butyraldehyde, 1-butene and n-butanol were compared with model predictions using the Black et al. mechanism. In general, the predicted trends for species concentrations are consistent with measurements. Sensitivity analyses and rate of production analyses were used to identify reactions important for predicting ignition delay time and the intermediate species time histories. Modifications to the mechanism by Black et al. were explored based on recent contributions to the literature on the rate constant for the key reaction, n-butanol+OH. The results improve the model agreement with some species; however, the comparison also indicates some reaction pathways, particularly those important to ethene formation and removal, are not well captured.     

Enhanced temperature-independent magnetoresistance below the metal-insulator transition temperature of epitaxial La0.2Nd0.4Ca0.4MnO3 thin films

Epitaxial La_0.2Nd_0.4Ca_0.4MnO₃ thin films have been deposited at 800°C on LaAlO₃ substrate using pulsed laser deposition technique. The structural and magnetotransport properties of the films have been studied. The sharp peak in the temperature dependence of the resistance corresponding to metal-to-insulator transition (T _p) has been observed at a temperature of T _p=82 K, 97 K and 110 K for 0 Oe, 20 kOe and 40 kOe magnetic fields, respectively. The film exhibits a large nearly temperature-independent magnetoresistance around 99% in the temperature regime below T _p. The zero field-cooled (ZFC) and field-cooled (FC) magnetization data at 50 Oe shows irreversibility between the ZFC and FC close to the ferromagnetic transition temperature T _c=250 K. The ZFC temperature data of the film displays ferromagnetic behavior for higher temperature regime T _c=250 K>T>T _p=82 K, and a decrease in magnetization with decreasing temperature up to 5 K below 82 K exhibiting a sort of antiferromagnetic behavior in the low temperature regime (T<82 K=T _p=T _N).     

Temperature hysteretic effect and its influence on colossal magnetoresistance of La0.33Nd0.33Ca0.33MnO3

Electrical resistance (R) measurements of a bulk La_0.33Nd_0.33Ca_0.33MnO₃ perovskite in magnetic fields up to 40 kOe have revealed anomalous temperature hysteretic effects both in 0 Oe and 20 kOe magnetic fields. The sharp peak observed in the R vs. T plot indicates the occurrence of metal-to-insulator (M-I) transition at a temperature of T _MI=110 K and 140 K, for cooling and warming paths, respectively. An applied magnetic field of 20 kOe reduces the resistance and shifts T _MI to 160 K and 185 K for cooling and warming, respectively. We have observed a much higher resistance in the cooling path than in the warming path leading to the hysteretic resistance ratio (R _cool/R _warm) of 200 at 110 K and 1.8 at 160 K for 0 Oe and 20 kOe, respectively. Record values of colossal magnetoresistance (CMR) have been achieved. The CMR value reaches nearly 99% in the temperature ranges of 90 K to 140 K and 90 K to 170 K for 20 kOe and 40 kOe magnetic fields in the cooling mode, respectively. The observed unusual behavior is attributed to the co-existence of La-rich and Nd-rich domains assumed to be distributed randomly in the compound.     

A novel intramolecular redox reaction: the transformation of L-proline to N-amino-2-pyrrolidones via a mesoionic system

The mesoionic derivative of N-nitrosoproline (2), reacts with PhCCCOOH and TFA to form the N-amino-2-pyrrolidones 4 and 5 respectively. Compounds 4 and 5 are formed in good yield by a novel intramolecular redox process, and their structures were determined by x-ray diffraction.     

Silica-coated nanocomposites of magnetic nanoparticles and quantum dots

Quantum dots (QDs) and magnetic nanoparticles (MPs) are of interest for biological imaging, drug targeting, and bioconjugation because of their unique optoelectronic and magnetic properties, respectively. To provide for water solubility and biocompatibility, QDs and MPs were encapsulated within a silica shell using a reverse microemulsion synthesis. The resulting SiO2/MP-QD nanocomposite particles present a unique combination of magnetic and optical properties. Their nonporous silica shell allows them to be surface modified for bioconjugation in various biomedical applications.