Tetrahydrogestrinone: discovery, synthesis, and detection in urine

Tetrahydrogestrinone (18a-homo-pregna-4,9,11-trien-17beta-ol-3-one or THG) was identified in the residue of a spent syringe that had allegedly contained an anabolic steroid undetectable by sport doping control urine tests. THG was synthesized by hydrogenation of gestrinone and characterized by mass spectrometry and NMR spectroscopy. We developed and evaluated sensitive and specific methods for rapid screening of urine samples by liquid chromatography/tandem mass spectrometry (LC/MS/MS) of underivatized THG (using transitions m/z 313 to 241 and 313 to 159) and gas chromatography/high-resolution mass spectrometry (GC/HRMS) analysis of the combination trimethylsilyl ether-oxime derivative of THG (using fragments m/z 240.14, 254.15, 267.16, and 294.19). A baboon administration study showed that THG is excreted in urine.     

Lithium bromide in acetonitrile: Thermodynamics,theory, and simulation

A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere.     

Recent Advances in Polyallenes: Preparation,Self-Assembly,and Stimuli-Responsiveness

Polyallenes, as a typical type of reactive polymers, are of great significance and have aroused widespread interest because they contain double bonds that can be post-modified into other functionalities to afford varieties of functional materials. This Minireview firstly highlights the recent advances in the preparation of polyallenes, including preparation of helical polyallenes through directly polymerization of chiral allene monomers or helix-sense-selective polymerization (HSSP) of achiral allene monomers, synthesis of 1,2-regulated polyallenes and 2,3-regulated polyallenes via selective polymerization of allene monomers, polymerization of allene monomers catalyzed by Ni(II)-terminated poly(3-hexylthiophene) (P3HT), and so on. Then, latest progress on the self-assembly and stimuli-responses of polyallene-based diblock, ABA and ABC triblock copolymers is summarized. We hope this Minireview will inspire more interest in developing polyallenes and encourage further advances in functional materials.     

Homoaromaticity and homoconjugation in the quinacenes: Biquinacene,triquinacene, and hexaquinacene

A thermodynamic criterion for aromatic and conjugative interactions is proposed. Enthalpies of stepwise hydrogenation of, for example, three double bonds are compensated for strain energy changes during hydrogenation. Strain energies are calculated by molecular mechanics. If the compensated values show a monotonic increase from bond 3 to bond 1, the molecule is conjugatively stabilized. If the initial rise is sharp followed by a constant H _h for bonds 2 and 1 and the molecule is cyclic, stabilization is aromatic. If the compensated H _h decreases, the interaction is destabilizing. By this set of criteria, biquinacene is unstabilized, triquinacene is homoaromatically stabilized, hexaquinacene is homoconjugatively stabilized, and cis,cis,cis-1,4,7-cyclononatriene is homoaromatically destabilized. New experimental data are presented for the biquinacenes (bicycloocta-1,7-diene and its hydrogenation products) and the hexaquinacenes.     

Perfluoropyridine: Discovery,Chemistry, and Applications in Polymers and Material Science

Perfluoropyridine (PFPy) is an organofluorine compound that has been employed for a variety of applications, from straightforward chemical synthesis to more advanced functions, such as fluorinated networks and polymers. This can be directly attributed to the highly reactive nature of PFPy, especially towards nucleophilic aromatic substitution (SNAr). The aim of this review is to highlight the discovery and synthesis of PFPy, discuss its reactive nature towards SNAr, and to summarize known reports of the utilization and thermal analysis of PFPy containing fluoropolymers and fluorinated network materials.     

Guanidinophosphazenes: design, synthesis, and basicity in THF and in the gas phase

A principle for creating a new generation of nonionic superbases is presented. It is based on attachment of tetraalkylguanidino, 1,3-dimethylimidazolidine-2-imino, or bis(tetraalkylguanidino)carbimino groups to the phosphorus atom of the iminophosphorane group using tetramethylguanidine or easily available 1,3-dimethylimidazolidine-2-imine. Seven new nonionic superbasic phosphazene bases, tetramethylguanidino-substituted at the P atom, have been synthesized. Their base strengths are established in tetrahydrofuran (THF) solution by means of spectrophotometric titration and compared with those of eight reference superbases designed specially for this study, P2- and P4-iminophosphoranes. The gas-phase basicities of several guanidino- and N',N',N',N'-tetramethylguanidino (tmg)-substituted phosphazenes and their cyclic analogues are calculated, and the crystal structures of (tmg)3P=N-t-Bu and (tmg)3P=N-t-Bu x HBF4 are determined. The enormous basicity-increasing effect of this principle is experimentally verified for the tetramethylguanidino groups in the THF medium: the basicity increase when moving from (dma)3P=N-t-Bu (pKalpha = 18.9) to (tmg)3P=N-t-Bu (pKalpha = 29.1) is 10 orders of magnitude. A significantly larger basicity increase (up to 20 powers of 10) is expected (based on the high-level density functional theory calculations) to accompany the similar gas-phase transfer between the (dma)3P=NH and (tmg)3P=NH bases. Far stronger basicities still are expected when, in the latter two compounds, all three dimethylamino (or tetramethylguanidino) fragments are replaced by methylated triguanide fragments, (tmg)2C=N-. The gas-phase basicity (around 300-310 kcal/mol) of the resulting base, [(tmg)2C=N-]3P=NH, having only one phosphorus atom, is predicted to exceed the basicity of (dma)3P=NH by more than 40 powers of 10 and to surpass also the basicity of the widely used commercial [(dma)3P=N]3P=N-t-Bu (t-BuP4) superbase.     

Immunosensors in Biology and Medicine: Analytical Capabilities, Problems, and Prospects

The current status of research in immunosensors was considered. Primary attention was focused on electrochemical, piezoelectric, and optical immunosensors. The analytical capabilities of these devices were discussed. The applicability of these immunosensors to solving various analytical problems in medicine and pharmacology in particular, was demonstrated. The prospects for the further development of immunosensor technologies were shown.     

Polymer chemistry in flow: New polymers,beads, capsules,and fibers

The union between polymer science and microfluidics is reviewed. Fluids in microreactors allow the synthesis of a wide range of polymeric materials with unique properties. We begin by discussing the important fluid dynamics that dominate the behavior of fluids on the micrometer scale. We then progress through a comprehensive analysis of the polymeric materials synthesized to date. This highlight concludes with an overview of the methods used to make microreactors. We enthusiastically endorse microreactors as a powerful approach to making materials with controlled properties, although we have tried to provide a critical eye to help the nonexpert enter the field. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6505–6533, 2006     

Chiral metallacyclophanes: self-assembly, characterization, and application in asymmetric catalysis

[structure: see text] A family of chiral metallacyclophanes has been readily assembled based on robust Pt-acetylide linkage and characterized by a variety of spectroscopic techniques and X-ray crystallography. The steric congestion around the chiral dihydroxy groups in rigid metallacyclophane 4 prevents their reactions with Ti(O(i)()Pr)(4) to form active catalysts for enantioselective diethylzinc additions to aromatic aldehydes. In contrast, chiral dihydroxy groups in more flexible unclosed metallacyclophane 5 are effective ligands for enantioselective catalytic diethylzinc additions to aromatic aldehydes.     

Advanced Developments in Cyclic Polymers: Synthesis,Applications, and Perspectives

Due to the topological effect, cyclic polymers demonstrate different and unique physical and biological properties in comparison with linear counterparts having the same molecular-weight range. With advanced synthetic and analytic technologies, cyclic polymers with different topologies, e.g. multicyclic polymers, have been reported and well characterized. For example, various cyclic DNA and related structures, such as cyclic duplexes, have been prepared conveniently by click chemistry. These types of DNA have increased resistance to enzymatic degradation and have high thermodynamic stability, and thus, have potential therapeutic applications. In addition, cyclic polymers have also been used to prepare organic–inorganic hybrids for applications in catalysis, e.g. catalyst supports. Due to developments in synthetic technology, highly pure cyclic polymers could now be produced in large scale. Therefore, we anticipate discovering more applications in the near future. Despite their promise, cyclic polymers are still less explored than linear polymers like polyolefins and polycarbonates, which are widely used in daily life. Some critical issues, including controlling the molecular weight and finding suitable applications, remain big challenges in the cyclic-polymer field. This review briefly summarizes the commonly used synthetic methodologies and focuses more on the attractive functional materials and their biological properties and potential applications.     

A gas-diffusion gold-ring-tip: Fabrication,characterization, and application in electrocatalysis

A gas-diffusion gold-ring microelectrode used as scanning electrochemical microscopy tip was fabricated. Compared to the ring-tip for droplet dispensation reported before, the as-fabricated micropipette tip has a larger ring size (ca. 25 μm diameter) that is beneficial to gas dispensation and is more sensitive to electroactive species. This micropipette electrode functioned as both a normal SECM tip and a gas dispenser was demonstrated by imaging FcMeOH⁺/FcMeOH reaction and electrocatalytic oxygen reduction reaction, respectively.     

Benzylic manganese halides, sulfonates, and phosphates: preparation, coupling reactions, and applications in organic synthesis

The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.     

Polyamidoamine dendrimer and dextran conjugates: preparation,characterization, and in vitro and in vivo evaluation

Amide and ester conjugates of aceclofenac with polyamidoamine (PAMAM-G0) dendrimer zero generation and dextran (40 kDa) polymeric carrier, respectively, are presented. The prepared conjugates were characterized by UV, TLC, HPLC, IR, and ¹H NMR spectroscopy. The average degrees of substitution of amide and ester conjugates were determined and found to be (12.5 ± 0.24) % and (7.5 ± 0.25) %, respectively. The in vitro hydrolysis studies showed that dextran ester conjugate hydrolyzed faster in a phosphate buffer solution of pH 9.0 as compared to PAMAM dendrimer G0 amide conjugate, and followed the first order kinetics. No amount of the drug was regenerated at pH 1.2 in simulated gastric fluid. The dextran conjugate showed short half-life as compared to the PAMAM dendrimer conjugate. Anti-inflammatory and analgesic activities of the dendrimer conjugate were found to be similar to those of the standard drug. Results of chronic ulceroginic activity showed deep ulceration and high ulcer index for aceclofenac, whereas lower ulcer index was found for the PAMAM dendrimer and dextran (40 kDa) conjugates. Experimental data suggest that PAMAM dendrimer and dextran (40 kDa) can be used as carriers for the sustained delivery of aceclofenac along with a remarkable reduction in gastrointestinal toxicity.     

ChemInform Abstract: Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF,BiOCl, BiOBr,and BiOI.

Study by using hybrid DFT with explicit treatment of spin—orbit coupling effects and dispersion interactions.     

Uncertainty evaluation in proficiency testing: state-of-the-art, challenges, and perspectives

The evaluation of measurement uncertainty, and that of uncertainty statements of participating laboratories will be a challenge to be met in the coming years. The publication of ISO 17025 has led to the situation that testing laboratories should, to a certain extent, meet the same requirements regarding measurement uncertainty and traceability. As a consequence, proficiency test organizers should deal with the issues measurement uncertainty and traceability as well. Two common statistical models used in proficiency testing are revisited to explore the options to include the evaluation of the measurement uncertainty of the PTRV (proficiency test reference value). Furthermore, the use of this PTRV and its uncertainty estimate for assessing the uncertainty statements of the participants for the two models will be discussed. It is concluded that in analogy to Key Comparisons it is feasible to implement proficiency tests in such a way, that the new requirements can be met. Received: 29 September 2000 Accepted: 3 December 2000