Simple preparation of 3I-O-substituted beta-cyclodextrin derivatives using cinnamyl bromide

[reaction: see text] A new method for preparation of 3(I)-O-substituted beta-cyclodextrin derivatives was developed. Cinnamyl bromide reacts with beta-cyclodextrin to form predominantly the 3(I)-O-cinnamyl derivative (30% isolated yield, >90% regioselectivity). After protection of the remaining cyclodextrin hydroxyls by acetylation, the cinnamyl group can be easily transformed to many other groups (exemplified by transformation to 3(I)-O-carboxymethyl derivative). Substitution pattern in singly modified CDs was unambiguously determined by a combination of 2D NMR techniques.     

High-spin states in the <Superscript>97</Superscript>Tc nucleus

High-spin states in the ⁹⁷Tc nucleus have been studied by in-beam γ-ray spectroscopy with the reaction ⁸²Se(¹⁹F,4nγ) at 68 MeV incident energy. Excited states have been observed up to about 8 MeV excitation and spin 43/2. The observed level scheme is compared with results of shell model calculations. Received: 22 November 2002 / Accepted: 23 December 2002 / Published online: 18 March 2003 RID="a" ID="a"e-mail: bucurescu@tandem.nipne.ro RID="b" ID="b"Present address: INFN, Laboratori Nazionali di Legnaro, Legnaro, Italy. RID="b" ID="b"Present address: INFN, Laboratori Nazionali di Legnaro, Legnaro, Italy. RID="b" ID="b"Present address: INFN, Laboratori Nazionali di Legnaro, Legnaro, Italy. RID="c" ID="c"Present address: Università di Padova, Padova, Italy. Communicated by C. Signorini     

Acid catalyzed intramolecular attack of β‐phenylthioureido group on amide function. Parallel formation of thiodihydrouracil and 4‐iminothiodihydrouracil. Different pathways in the Edman degradation reaction in the formation of six‐ versus five‐membered cyclic intermediates

Contrary to the cleavage of α‐phenylthioureido peptides 1 proceeding through intermediate 2‐anilinothiazolinone 2 , the b‐analog cis‐2‐(3‐phenylthioureido)cyclopentane‐carboxamide 5 forms transiently 4‐imino‐2‐thioxopyrimidine 6 . Monitoring amide cyclization and hydrolysis of iminopyrimidine 6 in acid by UV showed that an equilibrium between 5 and 6 was reached followed by slower conversion of both compounds into 2‐oxo‐4‐thioxopyrimidine 7 . Both processes were characterized by isosbestic points, the first due to parallel conversion of 5 into 6 and 7 (or 6 into 5 and 7 ) at a constant ratio while the second identical for both reactants – to conversion of equilibrated 5 and 6 into 7 . The special isosbestic points allowed the determination of the individual constants of Scheme 2. Further confirmation was obtained from NMR product analysis and following the cyclization of amide 5 in DMSO:DCl. Product 2‐oxo‐4‐ thioxopyrimidine 7 hydrolyzed reversibly to thioureido acid 8 . The cyclization rate of 8 allowed the participation of 6‐oxothiazine 10 formed by sulfur attack to be excluded. The absence of sulfur attack in the six‐membered case is explained by the longer C? S bond bringing about greater bond angle strain at the tetrahedral ring atoms due to the geometrical characteristics of five‐ and six‐membered rings with planar segments. The cyclizations of amide 5 to iminopyrimidine 6 and to thiodihydrouracil 7 are first order in [H⁺], while the reactions of protonated imine 6 H⁺ are zero order to amide and ?1 to thiodihydrouracil. The reaction orders can be reconciled by assuming a rate determining proton transfer from the tetrahedral intermediate in amide cyclization. Copyright © 2007 John Wiley & Sons, Ltd.     

Lifetimes of some excited states in 64Ni, 66Zn and 68Zn

Mean lives and excitation energies of the lowest levels in⁶⁴Ni,⁶⁶Zn and⁶⁸Zn were measured with the aid of the (α, α′γ) and (α, pγ) reactions. The γ-rays were detected in coincidence with the outgoing particles. The following mean lives were determined from DSA measurements: 400 ± 150 fs for the level at E_x = 1.35 MeV in ⁶⁴Ni; 270 ± 100, 210 ± 110, 330 ± 200, 80 ± 70 fs for the levels at E_x = 1.87, 2.45, 2.83, 2.94 MeV in ⁶⁶Zn, and 1300 ± 300, > 160, 600 ± 200 fs for the levels at E_x = 1.08, 1.89 and 2.76 MeV in ⁶⁸Zn, respectively.     

A Particulate Biochromatographic Support for the Research of Arginase Inhibitors Doped with Nanomaterials: Differences Observed Between Carbon and Boron Nitride Nanotubes. Application to Three Plant Extracts

The arginase enzyme was bound to porous silica using a reactive polymer where two types of nanomaterials were entrapped, i.e., carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs). For the first time, it was shown that BNNTs were highly efficient for increasing the performance of a particulate bioactive support. Also, we demonstrated that BNNTs enhanced more strongly this effect in comparison with CNTs. In addition, with this novel bioactive support, the relative IC50 values of the well-known arginase inhibitors were found to be in agreement with those derived by the conventional spectrometric method. It was shown the ethylacetate extract of the roots of Spirotropis longifolia (SL) and of the ethanol extract of sunflower (Helianthus annuus) seed (SS) and Lonicera japonica Thunb, i.e., honeysuckle (H) on the arginase activity inhibited the enzyme activity.

     

Development of non-deterioration-type skin tissue phantom using silicone material

We developed a new type of three-layered skin tissue phantom using silicone material. This phantom maintains its optical properties in a certain period of time, typically about three months, which is much longer than about 30 min with our previous agar-type phantom. Experiments on spectral reflectance measurements and color analysis indicate the possibility of silicone-type skin tissue phantom.     

Synthesis of new (arylcarbonyloxy)aminopropanol derivatives and the determination of their physico-chemical properties

Eight hydrochlorides of 3-{2-[(2/4-fluorophenoxy)-ethylamino]}-2-hydroxypropyl-4-alkoxybenzoates and four hydrochlorides of 3-tert-butylamino-2-hydroxypropyl-4-butoxybenzoates were prepared as potential antagonists of the β₁-adrenergic receptor (beta-blockers). A multistep synthesis of these compounds is described as well as their detailed analytical characterization. The pharmacokinetic properties of these weak base compounds are significantly influenced by their acid-base dissociation constant, pK _a. The knowledge of this value is crucial for new drug development. This paper is aimed at developing a methodology that utilizes pH-dependent ¹H NMR spectroscopy for its routine analysis. The selected predicted physico-chemical parameters of the new (arylcarbonyloxy)aminopropanols (i.e., aryloxyaminopropanol derivatives) were compared with the model drugs esmolol and flestolol.      

Doxorubicin Encapsulation Investigated by Capillary Electrophoresis with Laser-Induced Fluorescence Detection

Doxorubicin (DOX) belongs to the group of anthracycline antibiotics with very effective anticancer properties. On the other hand, the cardiotoxic effects limit its application over the maximum cumulative dose. To overcome this obstacle, encapsulation of this drug into the protective nanotransporter such as apoferritin is beneficial. In this study, fluorescent behavior of DOX in various solvents was determined by fluorescence spectrometry, demonstrating the fluorescence quenching effect of water, which is often used as a solvent. It was found that by increasing the amount of the organic phase in the DOX solvent the dynamic quenching is significantly suppressed. Ethanol, acetonitrile and dimethyl sulfoxide were tested and the best linearity of the calibration curve was obtained when above 50 % of the solvent was present in the binary mixture with water. Moreover, pH influence on the DOX fluorescence was also observed within the range of 4–10. Two times higher fluorescence intensity was observed at pH 4 compared to pH 10. Further, the DOX behavior in capillary electrophoresis (CE) was investigated. Electrophoretic mobilities (CE) in various pH of the background electrolyte were determined within the range from 16.3 to −13.3 × 10 ⁻⁹ m⁻² V⁻¹ s⁻¹. Finally, CE was also used to monitor the encapsulation of DOX into the cavity of apoferritin as well as the pH-triggered release.