Enantioseparation of amino acid derivatives by capillary zone electrophoresis using vancomycin as chiral selector

The separation of racemic derivatized amino acids (N-acetyl) into their enantiomers was achieved using capillary zone electrophoresis employing vancomycin as a chiral selector. Due to the strong absorption properties of the chiral selector at the low wavelengths used, the partial-filling countercurrent method was adopted in order to improve method sensitivity. In the separation system studied, the chiral selector filled only a part of the capillary and, due to the appropriate selection of the pH, was moving in the opposite direction of the analytes keeping the detector free from absorbing compounds. The effect of several experimental parameters on the enantioresolution of analytes was studied, e.g., vancomycin concentration (0-5 mM), pH of the background electrolyte (pH 4-7), capillary temperature (15-35 degrees C), and the presence of an organic modifier in the run buffer (methanol or ethanol or n-propanol). N-Acetyl glutamic acid, serine, cystine, tyrosine, and proline were all baseline-resolved into their enantiomers and the enantioresolution factor (R(s)) was increased by raising the vancomycin concentration. pH 4 allowed the baseline resolution of the five studied analytes in the presence of 2.5 mM of chiral selector and an increase in pH caused a decrease of R(s).     

Synthesis of new bicyclic lactam peptidomimetics by ring-closing metathesis reactions

An efficient and versatile synthetic method for the preparation of new fused bicyclic lactams 3a and 3b is described. The spirane cyclopentane nucleus was easily installed by diallylation of the pyroglutamate derivative 18 followed by ring-closing metathesis (RCM). A more practical and stereoselective method for the allylation of the α-methoxy carbamate 21, involving the use of InCl₃ as a Lewis acid, was developed. In the crucial coupling reaction of the diastereomeric mixture of cis- and trans-pirrolidine derivatives 5a and 5b with N-Cbz vinyl phenylalanine only the cis isomer was found to react. An RCM reaction on the dipeptides 25a and 25b followed by catalytic hydrogenation, gave the final epimeric bicyclic lactams 3a and 3b. The same synthetic sequence on the model compound 7, lacking the spiro cyclopentane nucleus, is also reported.     

Sensorless Control of Induction Machines by a New Neural Algorithm: The TLS EXIN Neuron

This paper proposes two speed observers for high-performance induction machine drives, both adopting an online adaptation law based on a new total least-squares (TLS) technique: the TLS EXIN neuron. The first is a model reference adaptive system (MRAS) observer with a neural adaptive integrator in the reference model and a neural adaptive model trained online by the TLS EXIN neuron. This observer, presented in a previous article of the authors, has been improved here in two aspects: first, the neural adaptive integrator has been modified to make its learning factor vary according to the reference speed of the drive, second, a neural adaptive model based on the modified Euler integration has been proposed to solve the discretization instability problem in field-weakening. The second observer is a new full-order adaptive one based on the state equations of the induction machine, where the speed is estimated by means of a TLS EXIN adaptation technique. Both these observers have been provided with an inverter nonlinearity compensation algorithm and with techniques for the online estimation of the stator resistance of the machine. Moreover, a thorough theoretical stability analysis has been developed for them both, with particular reference to the field-weakening region behavior for the TLS MRAS observer and to the regenerating mode at low speeds for the TLS adaptive observer. Both speed observers have been verified in numerical simulation and experimentally on a test setup, and have also been compared experimentally with the BPN MRAS observer, the classic adaptive observer and with an open-loop estimator. Results show that both proposed observers outperform all other three observers in every working condition, with the TLS adaptive observer resulting in a better performance than the TLS MRAS observer     

Detection of Volatiles by HS-SPME-GC/MS and Biological Effect Evaluation of Buddha’s Hand Fruit

The present work aimed to chemically characterize and evaluate the antiradical power and biological effects of Citrus medica var. sarcodactylus essential oil (EO) and hydrolate (Hy) from exocarp as well as methanol extracts, from both exocarp and mesocarp (EEX and MEX). The whole fresh fruit was also investigated by SPME-GC/MS to describe its volatile composition. EO and Hy were analyzed by GC/MS and HS-GC/MS techniques, respectively. Limonene and γ-terpinene were found to be the most abundant compounds both in the fresh parts of the fruit and in the EO, while α-terpineol and terpinen-4-ol were in the Hy. The extracts were also rich in furan and coumarin derivatives. A good antiradical activity of all samples except Hy was detected both against ABTS·+ than DPPH·, removed up to about 50%. The antibacterial activity against Bacillus cereus and Escherichia coli was evaluated by microwell dilution method to determine MIC and MBC values. EEX and MEX showed efficacy at very high concentrations against both tested bacteria. The MIC value of EO against B. cereus was 0.5% v/v, while Hy was not able to inhibit the bacterial growth at the tested concentrations. Cytotoxicity investigated on the HL60 leukemia cell line by MTT assay provided an EC₅₀ of 1.24% v/v for EO. Interesting activity of Hy was also observed.     

A Bist Scheme for Non-Volatile Memories

A new BIST scheme for on-chip testing of non-volatile memories and based on signature analysis is presented. The signature of the whole memory, whose content can be changed selectively by the user, is dynamically self-learned by the memory and it is saved in a dedicated memory location. Either such a signature can be externally compared with the expected one in order to check for the programming operation, or it can be used for comparison purposes when data retention must be self-tested.     

Asymmetric base pairing in the complex 5-fluorocytosinium chloride/5-fluorocytosine monohydrate

The structure of the complex 5-Fluorocytosinium chloride/5-Fluorocytosine monohydrate has been studied by X-ray diffraction methods. It crystallizes in the monoclinic system, space group P 2₁ /n, a = 7.1257 (15), b = 8.351 (3), c = 21.520 (4) ?, β = 92.89 (8)°, V = 1279.0 (6) ?³, Z = 4. The structure consists of triple hydrogen-bonded 5-Fluorocytosine pairs, water molecules and chloride anions. Asymmetric reversed Watson-Crick base pairing occurs between one protonated (5FcytH⁺) and one neutral 5-Fluorocytosine (5Fcyt) molecule.     

A semiorthogonal decomposition for Brauer–Severi schemes

A semiorthogonal decomposition for the bounded derived category of coherent sheaves on a Brauer–Severi scheme is given. It relies on bounded derived categories of suitably twisted coherent sheaves on the base (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lower semicontinuity for quasiconvex integrals of higher order

We consider a functional of the type , where is an open bounded set of and F is a Carathéodory function. By an approximation argument we prove the lower semincontinuity of with respect to the weak topology of under p-growth conditions for the integrand F. Received November 8, 1997     

Measurement of the η production in proton-proton collisions with the COSY time-of-flight spectrometer

The reaction pp → ppη was measured at excess energies of 15 and 41 MeV at an external target of the Jülich Cooler Synchrotron COSY with the time-of-flight spectrometer. About 25000 events were measured for the excess energy of 15 MeV and about 8000 for 41 MeV. Both protons of the process ppη were detected with an acceptance of nearly 100% and the η was reconstructed by the missing-mass technique. For both excess energies the angular distributions are found to be nearly isotropic. In the invariant-mass distributions strong deviations from the pure phase space distributions are seen. Received: 24 May 2002 / Accepted: 20 September 2002 / Published online: 17 January 2003 RID="a" ID="a"e-mail: e.roderburg@fz-juelich.de Communicated by M. Gar?on