An iboga alkaloid chemotaxonomic marker from endemic Tabernaemontana ternifolia with antitubercular activity

Abstract

Coronaridine (1) was isolated from the CH₂Cl₂ root extract of Tabernaemontana ternifolia. The structure of 1 was established from 1D- and 2D-NMR and HR-ESIMS experiments, and by comparison with reported spectroscopic data. To date, this is the first report of compound 1 from T. ternifolia, introduced as new Tabernaemontana species from Philippines in 2005 on the basis of morphological characters. Coronaridine, an iboga-type indole alkaloid, has been isolated from over 50 Tabernaemontana species and can thus be inferred as a chemotaxonomic marker of the genus. T. ternifolia has a distinct arrangement of leaves not known in the genus, but is variable in other genera. Its isolation from endemic T. ternifolia establishes its position in the genus and supports the claim that coronaridine is a chemical marker of the genus Tabernaemontana. Interestingly, coronaridine exhibited relatively weak activity against Mycobacterium tuberculosis H₃₇Rv (MIC 82.64?μg/mL) (Rifampicin MIC 0.05?μg/mL).     

Development of a screening method to determine the pattern of fermentation metabolites in faecal samples using on-line purge-and-trap gas chromatographic–mass spectrometric analysis

An on-line screening method to analyse volatile organic compounds (VOCs) in faecal samples was developed. VOCs were isolated from a standard solution or faecal samples using a purge-and-trap system and identified and quantified by GC–MS. The experimental conditions were optimised and the performance of the system was evaluated. Linear calibration curves were obtained with correlation coefficients of at least 0.992. RSDs within and between days were less than 10%. The method was successfully applied to the analysis of faecal samples, yielding 135 different volatile organic compounds identified in 11 faecal samples. Of those, 22 VOCs were found in all volunteers, whereas 34 VOCs were person-specific.     

Energy-dispersive x-ray fluorescence analysis for sulphur,chlorine, potassium and calcium in aerosols

Problems in the use of x-ray spectrometry for the fast multi-element analysis of environmental samples such as aerosols collected on filters arise from absorption of the fluorescence intensity in the filter and in the collected matter. A procedure is described for the determination of the elements sulphur to calcium in aerosols collected on Whatman 41 filters. Two methods are compared for deconvolution of the spectra. These are based on counting in fixed energy channels or on non-linear least-squares analysis. Corrections for absorption effects have been calculated. Calibration is done with thin film standard deposits. The accuracy of the method is better than 15%. Difficulties in ascertaining the chlorine content of the filter are discussed. The evaporation of the chlorine fraction from the filter was studied in detail.     

Pseudo-likelihood methodology for partitioned large and complex samples

Large data sets, either coming from a large number of independent replications, or because of hierarchies in the data with large numbers of within-unit replication, may pose challenges to the data analyst up to the point of making conventional inferential methods, such as maximum likelihood, prohibitive. Based on general pseudo-likelihood concepts, we propose a method to partition such a set of data, analyze each partition member, and properly combine the inferences into a single one. It is shown that the method is fully efficient for independent partitions, while with dependent sub-samples efficiency is sometimes but not always equal to one. It is argued that, for important realistic settings, efficiency is often very high. Illustrative examples enhance insight in the method’s operation, while real-data analysis underscores its power for practice.     

Rotational Spectroscopy and Ring-Puckering Conformation of 3-Hydroxytetrahydrofuran

The microwave spectrum of 3-hydroxytetrahydrofuran was recorded using a Fourier transform microwave spectrometer; the rotational constants (MHz) are: A = 5581.8230(7), B = 3638.8316(7), and C = 2924.7410(7). Microwave spectra for four (13)C isotopic species were recorded in natural abundance. Stark effect measurements were used to determine the projections of the dipole moment on the principal inertial axes: μ(a) = 0.956(1) D, μ(b) = 0.875(2) D, μ(c) = 1.050(2) D, and μ(tot) = 1.667(2) D. The internal coordinates of the carbon and oxygen atoms were least-squares fit to the 15 moments of inertia, and the best-fit structure is a C(4')-endo envelope ring conformation, in good agreement with ab initio calculations (MP2/6-31Gdaggerdagger). Copyright 2000 Academic Press.     

Complementary influence of electric and magnetic fields on the sample voltage oscillations ofP-type ultrapure germanium

We report on a previously not observed behaviour of oscillations of the voltage over a hyperpure germanium sample, when increasing the sample current from 0.05 to 13 A, for a number of transverse magnetic fields ranging from 697 to 1746 gauss. The sample temperature was 7.54 K±0.02 K. For each magnetic field the first observed peaks in the frequency spectrum of the sample voltage go to chaos by the period-doubling route and simultaneously shift to lower frequencies (first scenario). Superimposed upon this chaotic spectrum a new peak emerges, which again shifts to lower frequencies with increasing sample current (second scenario). A complementary effect of the sample current and the magnetic field is detected for four properties: firstly, the sudden onset of high resistance in the current versus voltage diagram, secondly, the transition between the two frequency scenarios described above, thirdly the presence of certain frequencies in the sample voltage spectra and fourthly the occurrence of an amplitude maximum for the principal frequency of the first scenario. It is shown that the first two transitions are interrelated.     

Sensitive and specific post-column fluorimetric determination of diethylstilboestrol residues in extracts of urine and animal tissues at the 1-ppb level

A rapid method for the selective detection and quantitation of diethylstilboestrol (DES) residues at the 1 ppb level in extracts of urine and animal tissues is described. After selective extraction of the oestrogens, DES is analysed by high-performance liquid chromatography using an in-line specific photochemical reactor followed by oxidation to highly fluorescent products. The reaction products of DES were investigated by thin-layer chromatography (TLC). The specificity of the proposed method was compared with that of a reference TLC method on different extracts of animal origin.     

Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal–Organic Framework

Metal–organic frameworks (MOFs) enable the design of host–guest systems with specific properties. In this work, we show how the confinement of anthracene in a well‐chosen MOF host leads to reversible yellow‐to‐purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host–guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications.     

A generalization of inverse distance weighting and an equivalence relationship to noise-free Gaussian process interpolation via Riesz representation theorem

In this paper, we show the relationship between two seemingly unrelated approximation techniques. On the one hand, a certain class of Gaussian process-based interpolation methods, and on the other hand inverse distance weighting, which has been developed in the context of spatial analysis where there is often a need for interpolating from irregularly spaced data to produce a continuous surface. We develop a generalization of inverse distance weighting and show that it is equivalent to the approximation provided by the class of Gaussian process-based interpolation methods. The equivalence is established via an elegant application of Riesz representation theorem concerning the dual of a Hilbert space. It is thus demonstrated how a classical theorem in linear algebra connects two disparate domains.     

Using shared sell-through data to forecast wholesaler demand in multi-echelon supply chains

Operational forecasting in supply chain management supports a variety of short-term planning decisions, such as production scheduling and inventory management. In this respect, improving short-term forecast accuracy is a way to build a more agile supply chain for manufacturing companies. Demand forecasting often relies on well-established univariate forecasting methods to extrapolate historical demand. Collaboration across the supply chain, including information sharing, is suggested in the literature to improve upon the forecast accuracy of such traditional methods. In this paper, we review empirical studies considering the use of downstream information in demand forecasting and investigate different modeling approaches and forecasting methods to incorporate such data. Where empirical findings on information sharing mainly focus on point-of-sale data in two-level supply chains, this research empirically investigates the added value of using sell-through data originating from intermediaries, next to historical demand figures, in a multi-echelon supply chain. In a case study concerning a US drug manufacturer, we evaluate different methods to incorporate this data and consider both time series methods and machine learning techniques to produce multi-step ahead weekly forecasts. The results show that the manufacturer can effectively improve its short-term forecast accuracy by integrating sell-through data into the forecasting process and provide useful insights as to the different modeling approaches used. The conclusion holds for all forecast horizons considered, though it is most pronounced for one-step ahead forecasts. Therefore, our research provides a clear incentive for manufacturers to assess the forecast accuracy that can be achieved by using sell-through data.