Simultaneous determination of mitotane,its metabolite,and five steroid hormones in urine samples by capillary electrophoresis using β-CD2SDS1 complexes as hydrophobic compounds solubilizers

Mitotane is a cytotoxic drug used in the treatment of inoperable adrenocortical carcinoma, it inhibits steroidogenesis as well, and therefore monitoring the level of steroid hormones in patients treated with mitotane is a crucial point of therapy. Hence, we have developed a simple, fast, and efficient electrophoretic method combined with reverse polarity sweeping as online preconcentration technique and dispersive liquid–liquid microextraction for the simultaneous determination of mitotane, its main metabolite DDA, and five steroid hormones (progesterone, testosterone, epitestosterone, cortisol, and corticosterone) in urine samples. In addition, a new sample matrix consisting of β-CD₂SDS₁ complexes for a high hydrophobic compounds solubilization was developed. Approach based on the application of β-cyclodextrin and SDS complex of a ratio 2:1 allowed for hydrodynamic injection into the capillary of a solution containing both mitotane and other analytes. The detection limits of the analytes for the reverse polarity sweeping-dispersive liquid–liquid microextraction method were found to be in the range of 1.5–3 ng/mL, which were approximately 1000 times lower than in the conventional hydrodynamic injection (5 s, 0.5 psi) without any preconcentration procedure. All analytes were completely resolved in less than 13 min by uncoated silica capillary with an inner diameter of 75 μm (ID) × 60 cm. Electrophoretic separation was performed in reverse polarity with a voltage of –25 kV with a background electrolyte (BGE) consisting of 100 mM SDS, 25% ACN, 25 mM phosphate buffer (pH 2.5), and 7 mM β-cyclodextrin.     

Acylation of novobiocin by carboxylic acid anhydrides: preparation and characterization of semi-synthetic novenamines

The acylation of novobiocin by carboxylic acid anhydrides leading to preparation of three families of semi-synthetic acylated novenamine analogues is reported. ESI-MS was used to monitor the reaction progress and enabled the isolation of intermediate compounds that provided insights into the sequence of acylation steps during the reaction. The chemoselectivity of the reaction depends on the carboxylic acid anhydride. The potential of the acylated novenamine analogues as leads for the development of antibacterial agents is discussed.     

Highly enantioselective addition of phenylethynylzinc to aldehydes using aziridine-functionalized tridentate sulfinyl ligands

Diastereomerically pure tridentate heteroorganic ligands containing hydroxyl, sulfinyl and aziridine moieties as nucleophilic centers, capable of binding to various organometallic reagents, have been proven to be highly efficient catalysts in the enantioselective addition of phenylethynylzinc to aldehydes to give the desired products in very high yields (up to 95%) and with ee’s up to 90%. The influence of the stereogenic centers located on the sulfinyl sulfur atom and in the aziridine moiety on the stereochemical course of the reaction is also discussed.     

Digital holographic cameras and data processing for remote monitoring and measurements of mechanical parts

Fast growing technology and requirements for testing of different types of materials and devices require new methods and systems for investigation of their parameters. Among the quantities of high interest are shape, deformation, roughness, local materials constants, displacement, and strain fields of elements under load. In the paper, we present novel solutions for digital holographic cameras, which allow for remote monitoring and measurement of the above mentioned quantities at small mechanical objects or at restricted areas of interest at big structures. The systems have compact design, “black box” measurement approach, and allows for fast and accurate measurements performed directly at the element and often in outdoor environment. The principles of digital and optoelectronic reconstruction and phase manipulation are described together with the exemplary measurement results obtained by means of the cameras presented.     

Air-dispersion measurement by second-harmonic heterodyne interferometry

Interferometers with long optical paths in air usually require knowledge and control of air dispersion. In addition, the measurements at several wavelengths and the dispersion properties of air allow errors caused by air turbulence to be compensated for. An innovative technique for air-dispersion measurement is described for long-baseline ground-based stellar interferometers. The technique combines second-harmonic interferometry and heterodyne detection to permit high-resolution measurement even for low optical powers. Experimental results show measurements of air dispersion in good agreement with the values predicted from the Edlén equation.     

Diastereoselective synthesis of tetrahydrofurans via reaction of gamma,delta-epoxycarbanions with aldehydes

[reaction: see text] Hydroxymethyl-substituted tetrahydrofurans were prepared with high diastereoselectivity by reaction of the carbanion derived from 3,4-epoxybutyl phenyl sulfone with aldehydes in the presence of a mixture of lithium and potassium tert-butoxides. Initial formation of aldol-type adducts is a nondiastereoselective but reversible process; thus, subsequent formation of one main diastereoisomer is controlled by the relative rates of cyclization. The configuration of the carbon stereocenter at the oxirane ring is inverted in the course of the S(N)2 process, and two new centers are created diastereoselectively.     

Locking entanglement with a single qubit

We study the loss of entanglement of a bipartite state subjected to discarding or measurement of one qubit. Examining behavior of different entanglement measures, we find that entanglement of formation, entanglement cost, logarithmic negativity, and one-way distillable entanglement are lockable measures in that they can decrease arbitrarily after measuring one qubit. We prove that any convex and asymptotically noncontinuous measure is lockable. As a consequence, all the convex-roof measures can be locked. The relative entropy of entanglement is shown to be a nonlockable measure.     

Secure key from bound entanglement

We characterize the set of shared quantum states which contain a cryptographically private key. This allows us to recast the theory of privacy as a paradigm closely related to that used in entanglement manipulation. It is shown that one can distill an arbitrarily secure key from bound entangled states. There are also states that have less distillable private keys than the entanglement cost of the state. In general, the amount of distillable key is bounded from above by the relative entropy of entanglement. Relationships between distillability and distinguishability are found for a class of states which have Bell states correlated to separable hiding states. We also describe a technique for finding states exhibiting irreversibility in entanglement distillation.