Symmetry breaking for theBBP-couplings

The B-A system of CP molecule has been reinvestigated. The rotational structures in the (0, 0) and (1, 1) bands have been photographed in the second order of a 10.6 m grating with 25μ slit width. The molecular constants have been determined using a weighted least squares fit computer program. It is found that the spin-splitting constant in the B-state is negative and not positive as reported by previous workers. An accurate value ofα in the A-state could be determined. The present analysis also suggests that the spin-splitting constant in the ground state of CP should be positive, hence the assignment of theR ₁ andR ₂ orP ₁ andP ₂ branches in the B-X system of CP by Barwaldet al should be interchanged.     

Gram‐Scale Synthesis of Chiral Cyclopropane‐Containing Drugs and Drug Precursors with Engineered Myoglobin Catalysts Featuring Complementary Stereoselectivity

Engineered hemoproteins have recently emerged as promising systems for promoting asymmetric cyclopropanations, but variants featuring predictable, complementary stereoselectivity in these reactions have remained elusive. In this study, a rationally driven strategy was implemented and applied to engineer myoglobin variants capable of providing access to 1‐carboxy‐2‐aryl‐cyclopropanes with high trans‐(1R,2R) selectivity and catalytic activity. The stereoselectivity of these cyclopropanation biocatalysts complements that of trans‐(1S,2S)‐selective variants developed here and previously. In combination with whole‐cell biotransformations, these stereocomplementary biocatalysts enabled the multigram synthesis of the chiral cyclopropane core of four drugs (Tranylcypromine, Tasimelteon, Ticagrelor, and a TRPV1 inhibitor) in high yield and with excellent diastereo‐ and enantioselectivity (98–99.9% de; 96–99.9% ee). These biocatalytic strategies outperform currently available methods to produce these drugs.     

Ligand and Linkage Isomers of Bis(ethylthiocarbamato) Copper Complexes with Cyclic C6H8 Backbone Substituents: Synthesis,Characterization, and Antiproliferation Activity

A series of isomeric bis(alkylthiocarbamate) copper complexes have been synthesized, characterized, and evaluated for antiproliferation activity. The complexes were derived from ligand isomers with 3-methylpentyl (H₂L²) and cyclohexyl (H₂L³) backbone substituents, which each yield a pair of linkage isomers. The thermodynamic products CuL^2a/3a have two imino N and two S donors resulting in three five-member chelate rings (555 isomers). The kinetic isomers CuL^2b/3b have one imino and one hydrazino N donor and two S donors resulting in four-, six-, and five-member rings (465 isomers). The 555 isomers have more accessible Cu^II/I potentials (E_1/2=−811/−768 mV vs. ferrocenium/ferrocene) and lower energy charge transfer bands than their 465 counterparts (E_1/2=−923/-854 mV). Antiproliferation activities were evaluated against the lung adenocarcinoma cell line (A549) and nonmalignant lung fibroblast cell line (IMR-90) using the MTT assay. CuL^2a was potent (^A549EC₅₀=0.080 μM) and selective (^IMR-90EC₅₀/^A549EC₅₀=25) for A549. Its linkage isomer CuL^2b had equivalent A549 activity, but lower selectivity (^IMR-90EC₅₀/^A549EC₅₀=12.5). The isomers CuL^3a and CuL^3b were less potent with ^A549EC₅₀ values of 1.9 and 0.19 M and less selective with ^IMR-90EC₅₀/^A549EC₅₀ ratios of 2.3 and 2.65, respectively. There was no correlation between reduction potential and A549 antiproliferation activity/selectivity.     

Onion slice shaped assembled ZnS quantum wires

Ultra-narrow wurtzite ZnS quantum wires assembled towards an onion slice shape are synthesized in water using a simple hydrothermal procedure. Wires are formed through an oriented attachment mechanism from wurtzite ZnS spherical particles. Strong confinement effect originated from the narrow width was observed and holds promise for use in broad optoelectronic device application.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Heat transport in turbulent rayleigh-Benard convection

We present measurements of the Nusselt number N as a function of the Rayleigh number R in cylindrical cells with aspect ratios 0. 510(7) they are consistent with N = asigma-1/12R1/4+bsigma-1/7R3/7 as proposed by Grossmann and Lohse for sigma greater, similar2.     

Effect of spatial heterogeneity on level of rejuvenation in Ni80P20 metallic glass

Understanding the relation between spatial heterogeneity and structural rejuvenation is one of the hottest topics in the field of metallic glasses (MGs). In this work, molecular dynamics (MD) simulation is implemented to discover the effects of initial spatial heterogeneity on the level of rejuvenation in the Ni$_{80}$P$_{20 }$MGs. For this purpose, the samples are prepared with cooling rates of $10^{10}$ K/s-$10^{12}$ K/s to make glassy alloys with different atomic configurations. Firstly, it is found that the increase in the cooling rate leads the Gaussian-type shear modulus distribution to widen, indicating the aggregations in both elastically soft and hard regions. After the primary evaluations, the elastostatic loading is also used to transform structural rejuvenation into the atomic configurations. The results indicate that the sample with intermediate structural heterogeneity prepared with 10$^{11}$ K/s exhibits the maximum structural rejuvenation which is due to the fact that the atomic configuration in an intermediate structure contains more potential sites for generating the maximum atomic rearrangement and loosely packed regions under an external excitation. The features of atomic rearrangement and structural changes under the rejuvenation process are discussed in detail.     

Photoluminescence studies of the amphoteric behavior of carbon and germanium in GaAs

Recombination radiation due to an exciton bound to neutral donors and neutral acceptors in high purity vapor phase epitaxial GaAs is investigated using high resolution photoluminescence spectroscopy at liquid helium temperatures. It is found that those samples which show the presence of germanium acceptors also exhibit a strong residual donor referred to in the literature as X₃. Samples containing carbon acceptors however, do not show the presence of X₃. In the past X₃ has been identified by some groups as due to carbon on the gallium site. The work presented here sugests that the X₃ donor is associated with germanium. This identification of the X₃ donor is in agreement with a recent assignment based on the far infrared study of neutron transmuted GaAs.     

外电场下极性量子阱中杂质态结合能

我们用变分方法研究了外电场下量子阱中的杂质态结合能,计算中既考虑了电子同体纵光学声子和界面光学声子的相互作用又考虑了杂质中心同体纵光学声子和界面光学声子的相互作用。我们以GaAs/Al_0.3Ga_0.7As量子阱为例,讨论了结合能随杂质位置、阱宽和电场强度的变化规律。得到了电子-声子相互作用对杂质态结合能和斯塔克效应的修正是相当明显的。     

Estimation of the dynamical properties of polyurethane foam through use of Prony series

A system identification procedure is formulated for estimation of parameters associated with a dynamic model of a single-degree-of-freedom foam-mass system. The foam is modelled as a linear viscoelastic material, whose constitutive law is expressed by an exponential hereditary relaxation kernel. The identification procedure is based on modelling the free response of the system as a Prony series (sum of exponentials terms) and fitting this Prony series to the data. This estimated response model is then utilized to estimate the parameters in the system model based on an explicit solution of the model. The procedure is analyzed for its reliability under different sources of error and uncertainties, such as the presence of weak components and experimental noise, and some modifications are evaluated to improve the robustness of the procedure. Finally, the procedure is applied to experimental data to obtain relevant stiffness, viscous and viscoelastic parameters associated with the system. Variations in values of these parameters as a function of static compression are also investigated.