Why not using capillary electrophoresis in drug analysis?

CE and related methods are well-established techniques in the analysis of biomolecules, such as DNA and proteins. Even though CE is a rather good alternative to HPLC for the evaluation of the impurity profile and the enantiomeric purity of a drug, it is rarely applied. This might be due to the reservation of national licensing authorities and the pharmacopoeia commissions for several reasons. In this review containing some experimental data we report on several drug examples which demonstrate the superiority of CE over HPLC in special cases, i.e., in the analysis of antibiotics, amino acids and peptides, and the determination of enantiomeric purity. However, in order to make the CE techniques more suitable for pharmacopoeial purposes the general methods describing separation methods have to be complemented with the adjustment of the electrophoretic conditions being necessary to satisfy the system suitability criteria without fundamentally modifying the methods. Taken together CE should be more often applied in drug quality control.     

Photocycle of 13-cis-retinal in bacteriorhodopsin caused by destruction to the cooperative effect of purple membrane

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High-pressure access to the Δ9-cis- and Δ9-trans-tetrahydrocannabinols family

Diels-Alder reactions of a range of 1-(alkoxy/alkyl-substituted phenyl)buta-1,3-dienes with methyl vinyl ketone and methyl acrylate carried out in ethanol as the reaction medium under 9 kbar pressure were investigated. The use of high pressure as the activating method of the Diels-Alder reactions allows the efficient and endodiastereoselective generation of a series of cis-cyclohexenyl-benzene cycloadducts, which are selectively converted into their trans-epimers. The cis-cyclohexenyl-benzenes and trans-cyclohexenyl-benzenes produced are useful precursors for accessing substituted privileged cis-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene and trans-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene skeletons. The total syntheses of Δ(9)-cis-tetrahydrocannabinol (THC) and Δ(9)-trans-THC, through the use of selected Diels-Alder adducts, are described. Finally, a route for obtaining Δ(9)-trans-THC in both enantiomeric pure forms based on the (S)-(-)-1-amino-2-(methoxymethyl)pyrrolidine (SAMP)-hydrazone method is also reported.     

To be,or not to be…Electrochemist?

Journal of Solid State Electrochemistry -     

First Total Synthesis of 12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one

12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one 9 was isolated from the twigs ofCroton salutaris1. Many diterpenes exhibit significant bioactivities, such as antibac-terial and antitumour and 9 has a rare structure. In order to study the relationshipb…     

A future for nuclear analytical techniques? Why not?

The choices of universities and national research institutions in supporting scientific research are increasingly justified on the basis of, amongst others, the relevance that has to be reflected by external, preferably sustainable funding of the research programs. Many traditional fields of application such as environmental sciences do not offer a promising outlook in this respect. As a consequence, university research reactors face closure because of reallocations of university funds to more contemporary sciences such as molecular biology and nanotechnology. Therefore, laboratories operating nuclear analytical techniques (NAA, (TR)XRF, and PIXE) need to use their creativity in finding ways for participation in, for example, nanotechnology, cancer research, or genomics. This requires an open mind in terms of the opportunities, strengths, and weaknesses of the techniques, and a departure of technique-oriented research towards problem-oriented research in which other nuclear techniques can be used. The unique features of radiotracers, nuclear imaging, and nuclear beam techniques are discussed in view of the new areas mentioned above. Some examples of opportunities for nuclear analytical techniques in the above-mentioned fields are given.     

Mometasone furoate revisited,or how did the hydrate get in the bottle?

The redetermined structure of 9α,21‐dichloro‐11β,17α‐dihydroxy‐16α‐methyl‐3,20‐dioxopregna‐1,4‐dien‐17‐yl furan‐2‐carboxylate monohydrate, C₂₇H₃₂Cl₂O₇·H₂O, at 100 K has triclinic (P1) symmetry. The structure displays O—H...O hydrogen bonding, which gives rise to infinite sheets extending parallel to the [110] plane. The previously published structure [Chen et al. (2005). J. Pharm. Sci. 94 , 2496–2509] was determined at room temperature and no significant anomalous signal was present. Data for the structure presented in this study were collected at low temperature and the absolute configuration could be established based solely on anomalous diffraction. Another point of interest is that the structure determined in this study is that of the monohydrate, even though the crystal was harvested from a bottle of nasal spray that was supposed to contain exclusively crystals of the anhydrous form.     

Why is the linking C-C bond in tetrahedranyltetrahedrane so short?

[structure: see text]. The block-localized wave function (BLW) method has been employed to probe the origin of the very short linking C-C bond (1.436 A) in tetrahedranyltetrahedrane. Computations show that the vicinal hyperconjugative interactions between the two tetrahedranyl groups is stronger than the conjugation in butadiene, and if there were no hyperconjugation effect, the bond distance would be 1.491 A. Thus, both the hybridization mode and hyperconjugative interactions contribute to the shortening of the central C-C bond in tetrahedranyltetrahedrane.     

Why does Kevlar decompose, while Nomex does not, when treated with aqueous chlorine solutions?

Kevlar and Nomex are high-performance polymers which have wide varieties of applications in daily life. Recently, they have been proposed to be biocidal materials when reacted with household bleach (sodium hypochlorite solution) because they contain amide moieties which can be chlorinated to generate biocidal N-halamine functional groups. Although Nomex can be chlorinated without any significant decomposition, Kevlar decomposes under the same chlorination conditions. In this study, two mimics for each of the polymers were synthesized to simulate the carboxylate and diaminophenylene components of the materials. It was found that the p-diaminophenylene component of the Kevlar mimic is oxidized to a quinone-type structure upon treatment with hypochlorous acid, which then decomposes. However, such a mechanism for the Nomex mimic is not possible. In this paper, based upon these observations, a plausible answer will be provided to the title question.     

Fluorescent or not? Size-dependent fluorescence switching for polymer-stabilized gold clusters in the 1.1-1.7 nm size range

The synthesis of fluorescent water-soluble gold nanoparticles by the reduction of a gold salt in the presence of a designed polymer ligand is described, the size and fluorescence of the particles being controlled by the polymer to gold ratio; the most fluorescent nanomaterial has a 3% quantum yield, a 1.1 nm gold core and a 6.9 nm hydrodynamic radius.     

An in vitro experiment on the interaction of charcoal or wheat bran with 11-nor-9-carboxy-Δ9-tetrahydrocannabinol and its glucuronide

The rather long yet variable terminal half-lives and detection times since last use of urinary cannabinoids may partly be attributed to their enterohepatic circulation which generally can be interrupted or restricted by chemical adsorbents. Therefore, an in vitro experiment was performed to study the adsorption/binding of 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC-COOH) and its glucuronide to activated charcoal and wheat bran; remaining concentrations were determined by liquid chromatography/tandem mass spectrometry. Adsorption/binding of 1,000 ng/mL of free or conjugated THC-COOH was complete using as little as 5 mg of charcoal whereas adsorption/binding to wheat bran increased with increasing amounts. Taking of remedies affecting enterohepatic recycling of THC-COOH and its glucuronide may challenge interpretation of cannabinoid concentrations used to detect or assess frequency of drug use or the time since last drug consumption.

Proteome-on-a-chip: mirage, or on the horizon?

Proteomics has emerged as the next great scientific challenge in the post-genome era. But even the most basic form of proteomics, proteome profiling, i.e., identifying all of the proteins expressed in a given sample, has proven to be a demanding task. The proteome presents unique analytical challenges, including significant molecular diversity, an extremely wide concentration range, and a tendency to adsorb to solid surfaces. Microfluidics has been touted as being a useful tool for developing new methods to solve complex analytical challenges, and, as such, seems a natural fit for application to proteome profiling. In this review, we summarize the recent progress in the field of microfluidics in four key areas related to this application: chemical processing, sample preconcentration and cleanup, chemical separations, and interfaces with mass spectrometry. We identify the bright spots and challenges for the marriage of microfluidics and proteomics, and speculate on the outlook for progress.     

Is there an unambigous answer to the question: Whether the aging program exists or not?

The article discusses up-to-date viewpoints on the reasons of aging in respect to their compliance with the concepts of programmed or stochastic aging.     

Do theories of the glass transition, in which the structural relaxation time does not define the dispersion of the structural relaxation, need revision?

Upon decreasing temperature or increasing pressure, a noncrystallizing liquid will vitrify; that is, the structural relaxation time, taualpha, becomes so long that the system cannot attain an equilibrium configuration in the available time. Theories, including the well-known free volume and configurational entropy models, explain the glass transition by invoking a single quantity that governs the structural relaxation time. The dispersion of the structural relaxation (i.e., the structural relaxation function) is either not addressed or is derived as a parallel consequence (or afterthought) and thus is independent of taualpha. In these models the time dependence of the relaxation bears no fundamental relationship to the value of taualpha or other dynamic properties. Such approaches appear to be incompatible with a general experimental fact recently discovered in glass-formers: for a given material at a fixed value of taualpha, the dispersion is constant, independent of thermodynamic conditions (T and P); that is, the shape of the alpha-relaxation function depends only on the relaxation time. If derived independently of taualpha, it is an unlikely result that the dispersion of the structural relaxation would be uniquely defined by taualpha.     

To D or not to D? On estimating the microenvironment polarity of biomolecular cavities

Knowledge of the local polarity of specific cavities in biopolymers can facilitate the design of selective low MW ligands that impact the structure and function of macromolecules. The most common tools for interrogating local polarity are fluorescent probes that are sensitive to their microenvironment. Researchers often evaluate and express this local polarity using dielectric constants, a parameter that reflects an inherent bulk property. A more appropriate expression should take into account solvent-solute interactions at the molecular level. Reevaluation of commonly used fluorophores illustrates the improved correlation between observed Stokes shift changes and E(T)(30) values as compared to the corresponding dielectric constants.     

Nature of "hydrogen bond" in the diborane-benzene complex: covalent, electrostatic, or dispersive?

Motivated by the recent discovery of unusual "hydrogen bonding"-like interaction between a borane system and benzene molecules in a molecular crystal, we carried out quantum mechanical calculations on a model complex, diborane-benzene cluster. The aim is to understand the nature of this unique interaction, which is expected to play an essential role in this novel class of molecular crystals. As analyzed in the present study, the interaction between diborane and benzene is special in the following aspects: (1) this interaction is mostly dispersive; (2) the observed pseudodirectionality with one of the diborane bridge hydrogen directed toward the benzene centroid minimizes the van der Waals contact; and (3) in the "hydrogen bond" map, this interaction is located in a unique region, which is presently populated by a few known molecular complexes with very different chemical characteristics. It is anticipated that the results from the present analysis will provide meaningful guidance for molecular engineering with diborane-benzene as a building block and for stabilization of this and possible other hydrogen bonds by dispersive contributions.