Total synthesis of (-)-rhazinilam: asymmetric C[bond]H bond activation via the use of a chiral auxiliary

The antitumor agent (-)-rhazinilam was synthesized in three major steps, namely the pyrrole synthesis, selective C[bond]H bond activation, and direct macrolactam formation. The key step involved asymmetric C[bond]H bond functionalization (dehydrogenation) of the diethyl group segment in intermediate 6. This was achieved by the attachment of chiral platinum complexes to the proximal nitrogen atom. A high degree of selectivity (60-75% ee) was achieved via the use of oxazolinyl ketone chiral auxiliaries.     

Symmetry-breaking defect in coupled dipole-proton system of hydrogen-bonded ferroelectric

We consider the coupled dipole-proton system of hydrogen-bonded ferroelectric crystal with one defect dipole that is coupled more strongly with the protons than the original dipole. This defect dipole simulates the symmetry-breaking defects that are often introduced in the crystals as probes in the electron paramagnetic resonance (EPR) experiments. A particular attention is paid to the explanation of strong isotope effects that have been detected in the measurements of static and dynamic properties of the pure crystals and the symmetry-breaking defects. We suppose that the isotope effects are caused by the isotope-dependent tunneling energy and we analyze behavior of the system with and without the defect in two adiabatic approximations that correspond to the case when the protons tunnel faster than the dipoles oscillate and to the opposite case. These two approximations lead to the two models which predict different properties the pure crystals and the symmetry-breaking defects.     

Affecting of aquatic vascular plant Lemna minor by cisplatin revealed by voltammetry

Within the context of application of platinum derivates based effective cytostatics, we can suppose that these risk metals can get into aquatic ecosystems where they can show biologic availability for food chain. In the present work we report on investigation of affecting of duckweed (Lemna minor) by various doses of cisplatin (0, 5, 10, 20, 40, 80 and 160 microM) for 4 days. The toxic influence of cisplatin was evaluated on the basis of growth inhibition expressed as number of leaves, growth rate, and total amount of biomass. The result value of 96hEC50, calculated from growth inhibition with comparison of growth rates, was 6.93 microM. Moreover we aimed on determination of cisplatin content using differential pulse voltammetry. The highest content of cisplatin (320 ng g(-1) of fresh weight) was determined in plants treated by 80 microM at the second day of treatment. Plants protect themselves against heavy metals by means of synthesis of cysteine-rich peptides such as glutathione and phytochelatins. Thus thiol determination in the treated plants by means of Brdicka reaction followed. The marked increase in thiol concentration detected is associated with defence reaction of the plant against stress caused by cisplatin.     

Longevity and other practical benefits of monolithic silica columns in the analysis of samples with complex matrices

At the turn of the millennium, the monolithic columns invoked new chances in HPLC. Even more than their organic polymer-based siblings, the inorganic silica-based monoliths targeted the territory of classical fully porous particle-packed columns, promising many benefits. Based on the number of published articles, the monoliths attracted academics just in the first few years after their introduction to the market. Lately, as superficially porous particles and sub-2-micron fully porous particles dominated the market, they stayed in the focus of routine laboratories and those who really appreciated the high porosity of the monolithic bed. The monoliths' practical benefits cannot be easily traced in the literature when they gradually lose academics' interest. Nevertheless, after more than 20 years of our experience, we still favor silica monoliths for their low back pressure and longevity when analyzing samples of clinical, pharmaceutical, and environmental origin. At the same time, the high permeability of monoliths enabled the birth of sequential injection chromatography, the medium-pressure separation technique based on the flexible flow manifold. This minireview aims to check, discuss, and summarize the practical aspects of monolithic silica columns in HPLC and medium-pressure sequential injection chromatography (SIC) that may not be visible at first sight but are evident retrospectively.     

HPLC methods for the determination of simvastatin and atorvastatin

We review high-performance liquid chromatography (HPLC) methods for the determination of two major statins used in clinical treatment – simvastatin and atorvastatin – in various fields of application, including bio-analytical assays, pharmaceutical assays and environmental applications.

Statin molecules are known to be susceptible to interconversion of the lactone and acidic forms, so it is necessary to consider this phenomenon during method development. We highlight liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) methods, as they have become a method of choice in bio-analytical and environmental applications. We compare the methods from the point of view of sensitivity. We discuss selection of the precursor ion for performing selected reaction monitoring (SRM) in MS detection and sample preparation.     

Charge transfer enhanced annihilation leading to deterministic single photon emission in rigid perylene end-capped polyphenylenes

Two new peryleneimide end-capped polyphenylenes are shown to be deterministic single photon sources in PMMA films due to efficient annihilation between charge transfer states.     

Sample Preparation for TLC — Genetic Algorithm-Based Optimization of Microwave-Assisted Extraction

JPC – Journal of Planar Chromatography – Modern TLC - Optimization of microwave-assisted extraction (MAE) as a method of sample preparation in thin-layer chromatographic (TLC) analysis...