Terracinolides A and B, Two Bishomoditerpene Lactones with a Novel Carbon Framework from Euphorbia terracina

A methanolic extract of Euphorbia terracina L. has been shown to contain two peracylated polyhydroxy terpenoid lactones with a novel C(22) carbon framework. These metabolites, which have been named terracinolides A (1) and B (2), are based on the same parent compound, but differ in the nature of one of the acyl residues. This novel skeletal system is formally derived from the jatrophane framework by addition of a two-carbon fragment on C-17 (jatrophane numbering).     

Linear stability analysis of oscillating Ekman boundary layers

The analysed Ekman layer is generated in a fluid layer rotating around an axis normal to its two bounding rigid plates. One of the plates is stationary, the other moving at certain Reynolds numbers. An additional oscillation is added to the moving plate at different amplitudes and frequencies. The linear stability of this system is determined via a Floquet analysis and a Galerkin-approximation of the corresponding Navier-Stokes-Equations. If the frequencies of the oscillations are small the critical Reynolds numbers of the Type I and Type II instabilities do not differ much from steady Ekman layers. Also for a purely oscillating system the critical values of the instabilities are almost consistent with those for a steady system. Interestingly, for higher frequencies the Type II instability does not appear any more. Instead the boundary layer becomes unstable only in terms of a Type I instability. In comparison with findings of other authors these results seem to be quite reasonable. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Zinc Oxide–Porphyrin Hybrid Rhombuses: Catalytically Active Microstructures via Self‐Assembly

A novel self‐assembled organic–inorganic hybrid structure consisting of zinc oxide and two oppositely charged porphyrins, showing significantly enhanced photocatalytic activity, is presented. Electrostatic self‐assembly of the cationic tetra‐(N‐methyl‐4‐pyridyl)porphyrin (TMPyP) with preformed assemblies of ZnO nanorods and the anionic tetra‐(4‐sulfonatophenyl)porphyrin (TPPS) in ethanol results in porphyrin microrhombuses decorated with ZnO nanorods. The structure formation is followed spectroscopically. The shape of the microrhombuses and the number of attached ZnO nanoparticles can be tuned through the porphyrin ratio TMPyP/TPPS. An enhanced and selective catalytic activity is found, giving insight into the degradation mechanism. Due to the tool‐box principle and its versatility, the concept may have great impact in fields such as solar‐energy conversion and optoelectronics.     

Selective Functionalization of Graphene at Defect‐Activated Sites by Arylazocarboxylic tert‐Butyl Esters

The development of versatile functionalization concepts for graphene is currently in the focus of research. Upon oxo‐functionalization of graphite, the full surface of graphene becomes accessible for C?C bond formation to introduce out‐of‐plane functionality. Herein, we present the arylation of graphene with arylazocarboxylic tert‐butyl esters, which generates aryl radicals after activation with an acid. Surprisingly, the degree of functionalization is related to the concentration of lattice vacancy defects in the graphene material. Consequently, graphene materials that are free from lattice defects are not reactive. The reaction can be applied to graphene dispersed in solvents and leads to bitopic functionalization as well as monotopic functionalization when the graphene is deposited on surfaces. As the arylazocarboxylic tert‐butyl ester moiety can be attached to various molecules, the presented method paves the way to functional graphene derivatives, with the density of defects determining the degree of functionalization.     

Spectrofluorimetric Method for Determination and Validation of Cefixime in Pharmaceutical Preparations Through Derivatization with 2-Cyanoacetamide

A simple, sensitive and accurate method has been developed for spectrofluorimetric determination of cefixime in pure form and pharmaceutical preparations. The method is based on the reaction of cefixime with 2-cyanoacetamide in the presence of 21% ammonia at 100 °C. The fluorescent reaction product showed maximum fluorescence intensity at λ 378 nm after excitation at λ 330 nm. The factors affecting the derivatization reaction were carefully studied and optimized. The fluorescence intensity versus concentration plot was rectilinear over the range of 0.02 to 4 μg mL⁻¹ with correlation coefficient of 0.99036. The limit of detection (LOD) and limit of quantification (LOQ) was found to be 2.95 ng mL⁻¹ and 9.84 ng mL⁻¹, respectively. The proposed method was validated statistically and through recovery studies. The method was successfully applied for the determination of cefixime in pure and dosage form with percent recoveries from 98.117% to 100.38%. The results obtained from the proposed method have been compared with the official HPLC method and good agreement was found between them.     

Spectrofluorimetric Protocol for Ceftriaxone in Commercial Formulation and Human Plasma After Condensation with Formaldehyde and Ethyl Acetoacetate

A new spectrofluorimetric method has been developed and validated for the quantification of ceftriaxone in bulk powder, pharmaceutical formulations and spiked human plasma. The developed method is reproducible, accurate, sensitive and cost effective. In this method, ceftriaxone was converted into a fluorescent compound by reacting with 0.8 M ethyl acetoacetate and 25% formaldehyde in a buffered medium (pH = 4.2) at 90 °C. The excitation and emission wavelengths of the fluorescent reaction product are 316 nm and 388 nm respectively. Optimization of the experimental conditions affecting the condensation reaction were carefully carried out and the optimum experimental conditions were incorporated in the procedure. The developed method has a broad linear range (0.2–20 μg mL⁻¹) with a correlation coefficient of 0.9992. The limit of detection (LOD) and limit of quantification (LOQ) was found to be 1.94 × 10⁻² μg mL⁻¹ and 6.47 × 10⁻² μg mL⁻¹ respectively. The common excipients and co-administered drugs were investigated for their interferences effect in the assay. The developed method was validated statistically through recovery studies and successfully applied to ceftriaxone determination in bulk powder, pharmaceutical formulations and spiked human plasma samples. The percent recoveries were found to be in the range of 99.04–100.26% for bulk powder, 98.88–99.92% for pharmaceutical formulations and 94.22–98.48% for spiked human plasma. The results were verified by comparing with reference literature HPLC method and were found in good agreement.     

Backward iteration in strongly convex domains

We prove that a backward orbit with bounded Kobayashi step for a hyperbolic, parabolic or strongly elliptic holomorphic self-map of a bounded strongly convex C² domain in Cd necessarily converges to a repelling or parabolic boundary fixed point, generalizing previous results obtained by Poggi-Corradini in the unit disk and by Ostapyuk in the unit ball of Cd.     

Biocatalytic organic synthesis of optically pure (S)-scoulerine and berbine and benzylisoquinoline alkaloids

A chemoenzymatic approach for the asymmetric total synthesis of the title compounds is described that employs an enantioselective oxidative C-C bond formation catalyzed by berberine bridge enzyme (BBE) in the asymmetric key step. This unique reaction yielded enantiomerically pure (R)-benzylisoquinoline derivatives and (S)-berbines such as the natural product (S)-scoulerine, a sedative and muscle relaxing agent. The racemic substrates rac-1 required for the biotransformation were prepared in 4-8 linear steps using either a Bischler-Napieralski cyclization or a C1-Cα alkylation approach. The chemoenzymatic synthesis was applied to the preparation of fourteen enantiomerically pure alkaloids, including the natural products (S)-scoulerine and (R)-reticuline, and gave overall yields of up to 20% over 5-9 linear steps.     

Spectrofluorimetric determination of cephradine in commercial formulation using ethylacetoacetate-formaldehyde as fluorogenic agent

A simple, precise and sensitive spectrofluorimetric method was developed for the determination of cephradine in pharmaceutical formulations. The method is based on reaction of cephradine with ethyl acetoacetate (EAA) in the presence of formaldehyde in acidic media. The fluorescence intensity of the resultant fluorescent derivative was measured at 443 nm after excitation at 350 nm. The effects of various experimental parameters on the formation of the fluorescent product were studied and optimized. A linear relationship between concentration of cephradine and fluorescence intensity was found over the range of 0.1–5.0 μg/mL. The limit of detection and quantification were calculated an found 1.09 × 10^?2 ± 3.64 × 10^?3 μg/mL and 3.64 × 10^?2 ± 3.64 × 10^?3 μg/mL, respectively and with relative standard deviation (RSD) 4.14%. Accuracy of the method was checked by standard addition method and applied to four different commercial formulations. The percentage recovery was found in the range of 97.03 to 103.80% for Velora suspension, 98.16 to 102.90% for velocef injection, 99.00 to 108.10% for Velora capsule and 99.06 to 104.90% for Cefradin capsule. The good percentage recoveries from all samples indicated that there were no interferences from the common excipients of formulations. The proposed method was successfully applied to the analysis of commercial suspension, capsule and injections. The result obtained by the proposed method was statistically validated with reference HPLC method. No significant difference in the results of the two methods was found regarding accuracy and precision using Student’s t-test and the variance ratio F-test.