Aromatic motifs in the design of Ephedra ligands for application in the asymmetric addition of diethylzinc to aldehydes and diphenylphosphinoylimines

Using N-benzylephedrine as a model, a collection of N-arylmethylephedrine derivatives has been prepared. These derivatives were prepared by treatment of ephedrine with selected aldehydes to create oxazolidines 8a–e. Reduction of the oxazolidines with lithium aluminum hydride afforded the target β-amino alcohols 9a–e. When applied in the catalytic asymmetric addition of diethylzinc to aldehydes and diphenylphosphinoylimines, the derivatives yielded product enantioselectivities that were comparable to those of N-benzylephedrine. An N-cyclohexylmethylephedrine derivative was also prepared; this β-aminoalcohol did not perform well in the catalytic addition of diethylzinc to 2-naphthaldehyde, thus suggesting that the aromatic motif is important in terms of maintaining a reasonable level of asymmetric induction. Finally, N-benzyl-N-methyl-2-amino-1,2-diphenyl-1-ethanol, an analogue of the N-benzylephedrine derivative, was prepared. This compound yielded comparable enantioselectivities in the catalytic asymmetric addition when employed as a ligand.     

On the Limited Stability of BDPA Radicals

1,3-Bis(diphenylene)-2-phenylallyl (BDPA)-based radicals are of interest as polarizing agents for dynamic nuclear polarization (DNP). For this purpose, a BDPA-nitroxide biradical, employing a phosphodiester linkage, was synthesized. Contrary to what is commonly assumed, BDPA-derived radicals were observed to have limited stability. Hence, the effects of various factors on the stability of BDPA radicals were investigated. Solvent polarity was found to play a significant role on degradation; a polar BDPA radical was observed to degrade faster in a non-polar solvent, whereas non-polar radicals were more unstable in polar solvents. The rate of decomposition was found to increase non-linearly with increasing radical concentration; a 2-fold increase in concentration led to a 3-fold increase in the rate of degradation. Collectively, these results indicate that the dimerization is a significant degradation pathway for BDPA radicals and indeed, a dimer of one BDPA radical was detected by mass spectrometry.     

Temporal synchronization of independently tunable single longitudinal mode hybrid CO2 lasers

We report a quantitative study of temporal synchronization of two independently tunable, single longitudinal mode, hybrid CO₂ lasers, sharing a common high pressure section. The theoretical estimates for the dependence of the laser pulse build up time on the cw section pressure are in satisfactory agreement with the experimental results. Further, we show that temporal synchronization over a larger frequency range with no significant degradation of peak power or longitudinal mode selection is possible, by utilising the cw section gain length and cavity Q as additional control parameters.     

Testing for Hermite Rank in Gaussian Subordination Processes

Statistical inference for time series with long-range dependence is often based on the assumption of Gaussian subordination X_t = G(Z_t). Although the Hermite rank m of G plays an essential role for statistical inference in these situations, the question of estimating m or of testing hypotheses about the Hermite rank has not been addressed in the literature. In this article, a method is introduced for testing H₀: m = 1 against H₁: m > 1. This allows for deciding whether inference based on the usual assumption of m = 1 is appropriate. Simulations and data examples illustrate the method.     

Nanosecond laser ablation for pulsed laser deposition of yttria

A thermal model to describe high-power nanosecond pulsed laser ablation of yttria (Y₂O₃) has been developed. This model simulates ablation of material occurring primarily through vaporization and also accounts for attenuation of the incident laser beam in the evolving vapor plume. Theoretical estimates of process features such as time evolution of target temperature distribution, melt depth and ablation rate and their dependence on laser parameters particularly for laser fluences in the range of 6 to 30 J/cm² are investigated. Calculated maximum surface temperatures when compared with the estimated critical temperature for yttria indicate absence of explosive boiling at typical laser fluxes of 10 to 30 J/cm². Material ejection in large fragments associated with explosive boiling of the target needs to be avoided when depositing thin films via the pulsed laser deposition (PLD) technique as it leads to coatings with high residual porosity and poor compaction restricting the protective quality of such corrosion-resistant yttria coatings. Our model calculations facilitate proper selection of laser parameters to be employed for deposition of PLD yttria corrosion-resistive coatings. Such coatings have been found to be highly effective in handling and containment of liquid uranium.     

Binding of chloroquine-conjugated gold nanoparticles with bovine serum albumin

We have conjugated chloroquine, an anti-malarial, antiviral and anti-tumor drug, with thiol-functionalized gold nanoparticles and studied their binding interaction with bovine serum albumin (BSA) protein. Gold nanoparticles have been synthesized using sodium borohydride as reducing agent and 11-mercaptoundecanoic acid as thiol functionalizing ligand in aqueous medium. The formation of gold nanoparticles was confirmed from the characteristic surface plasmon absorption band at 522 nm and transmission electron microscopy revealed the average particle size to be ~7 nm. Chloroquine was conjugated to thiolated gold nanoparticles by using EDC/NHS chemistry and the binding was analyzed using optical density measurement and Fourier transform infrared spectroscopy. The chloroquine-conjugated gold nanoparticles (GNP-Chl) were found to interact efficiently with BSA. Thermodynamic parameters suggest that the binding is driven by both enthalpy and entropy, accompanied with only a minor alteration in protein's structure. Competitive drug binding assay revealed that the GNP-Chl bind at warfarin binding site I in subdomain IIA of BSA and was further supported by Trp212 fluorescence quenching measurements. Unraveling the nature of interactions of GNP-Chl with BSA would pave the way for the design of nanotherapeutic agents with improved functionality, enriching the field of nanomedicine.     

The use of ECD/ETD to identify the site of electrostatic interaction in noncovalent complexes

Electrostatic interactions play an important role in the formation of noncovalent complexes. Our previous work has highlighted the role of certain amino acid residues, such as arginine, glutamate, aspartate, and phosphorylated/sulfated residues, in the formation of salt bridges resulting in noncovalent complexes between peptides. Tandem mass spectrometry (MS) studies of these complexes using collision-induced dissociation (CID) have provided information on their relative stability. However, product-ion spectra produced by CID have been unable to assign specifically the site of interaction for the complex. In this work, tandem MS experiments were conducted on noncovalent complexes using both electron capture dissociation (ECD) and electron-transfer dissociation (ETD). The resulting spectra were dominated by intramolecular fragments of the complex with the electrostatic interaction site intact. Based upon these data, we were able to assign the binding site for the peptides forming the noncovalent complex.     

Synthesis, structure and characterization of fac-[Re(CO)3] complexes derived from hydrazone Schiff bases: DFT-TDDFT investigation on electronic structures

The syntheses, structural and spectroscopic characterization of the complexes of general formula [ReL(CO)₃Cl] bearing bifunctional hydrazone Schiff base ligand L are presented in this paper. The structure of one of the complexes is determined by X-ray crystallography. The solid-state structure of the compound is involved in a secondary interaction in lattice forming a supramolecular array. The gas phase geometry optimization and electronic calculation have been performed using density functional theory without any symmetry constraints. On the basis of structural and theoretical studies, ligand in the complexes is considered to be in the keto, not in enol form. Experimental ground state IR and NMR data set agree with those calculated by DFT calculations. The electronic spectra of the complexes are calculated by time dependent density functional theory (TDDFT) using conductor like polarizable continuum model (CPCM). The computed vertical excitation energies in solution are in good agreement with experimental one showing that the metal-to-ligand charge transfer transitions in visible region dominate over ligand based ILCT transition. The TDDFT excited states calculation of the electronic spectra in solution provides evidence towards luminescence spectra.