RADICAUX LIBRES INDUITS PAR L''ACTION DU RAYONNEMENT ULTRAVIOLET SUR CERTAINS CONSTITUANTS DE L''ACIDE DEOXYRIBONUCLEIQUE

The action of ultra violet rays of 260 nm on aqueous solutions of bases, nucleosides and nucleotides of DNA at 77°K is studied by electron spin resonance. It is shown that the free radicals observed are similar, with a few noteworthy exceptions to those induced by X-rays, under the same conditions of temperature, in the solid state. Contrary to what might be excepted on the basis of the results obtained by X-rays, the variation in the yield in paramagnetic centres in each sequence studied does not seem to be important.     

ETUDE PAR RESONANCE PARAMAGNETIQUE ELECTRONIQUE DE LA PHOTOSENSIBILISATION DES ACIDES AMINES PAR LA PROFLAVINE

Abstract— –The photosensitization of amino acids by proflavine is studied using the technique of electron spin resonance spectroscopy. The analysis of the line shape as a function of the incident microwave power (both in the presence and absence of oxygen) and the dependence of the numbers of free radicals on the intensity of the incident light allow one to suggest that two types of radicals are formed. One is formed by a biphotonic process, the nature of the radicals being the same as in the case of ionising radiation, while the other is probably the RO₂ radical formed as a result of photodynamic action.     

A Popov-theory-based approach to digital H{infty} control with measurement feedback for Pritchard-Salamon systems

In this paper, we deal with the digital output-measurement-feedbackH control problem for Pritchard-Salamon infinite-dimensionalsystems with unbounded input and output operators. A discretePopov-theory-based solution is given in terms of the solvabilityof Kalman-Szegö-Popov-Yakubovitch systems associated withthe equivalent discrete-time time-invariant system obtainedby lifting the T-periodic continuous-time system.     

Second‐Generation Inhibitors for the Metalloprotease Neprilysin Based on Bicyclic Heteroaromatic Scaffolds: Synthesis,Biological Activity,and X‐Ray Crystal‐Structure Analysis

A new class of nonpeptidic inhibitors of the Zn^II‐dependent metalloprotease neprilysin with IC₅₀ values in the nanomolar activity range (0.034–0.30 μM ) were developed based on structure‐based de novo design (Figs. 1 and 2). The inhibitors feature benzimidazole and imidazo[4,5‐c]pyridine moieties as central scaffolds to undergo H‐bonding to Asn542 and Arg717 and to engage in favorable π‐π stacking interactions with the imidazole ring of His711. The platform is decorated with a thiol vector to coordinate to the Zn^II ion and an aryl residue to occupy the hydrophobic S1′ pocket, but lack a substituent for binding in the S2′ pocket, which remains closed by the side chains of Phe106 and Arg110 when not occupied. The enantioselective syntheses of the active compounds (+)‐ 1 , (+)‐ 2 , (+)‐ 25 , and (+)‐ 26 were accomplished using Evans auxiliaries (Schemes 2, 4, and 5). The inhibitors (+)‐ 2 and (+)‐ 26 with an imidazo[4,5‐c]pyridine core are ca. 8 times more active than those with a benzimidazole core ((+)‐ 1 and (+)‐ 25 ) (Table 1). The predicted binding mode was established by X‐ray analysis of the complex of neprilysin with (+)‐ 2 at 2.25‐Å resolution (Fig. 4 and Table 2). The ligand coordinates with its sulfanyl residue to the Zn^II ion, and the benzyl residue occupies the S1′ pocket. The 1H‐imidazole moiety of the central scaffold forms the required H‐bonds to the side chains of Asn542 and Arg717. The heterobicyclic platform additionally undergoes π‐π stacking with the side chain of His711 as well as edge‐to‐face‐type interactions with the side chain of Trp693. According to the X‐ray analysis, the substantial advantage in biological activity of the imidazo‐pyridine inhibitors over the benzimidazole ligands arises from favorable interactions of the pyridine N‐atom in the former with the side chain of Arg102. Unexpectedly, replacement of the phenyl group pointing into the deep S1′ pocket by a biphenyl group does not enhance the binding affinity for this class of inhibitors.     

Synthesis and mesomorphic properties of perfluorinated rod-like liquid crystals with sulphur-containing spacers

In order to determine the influence of 'sulphur-containing' spacers on the formation of mesophases in low molecular mass compounds, we have examined the mesomorphic behaviour of molecules which consists of a 4-biphenyl unit linked to an unbranched fluorinated chain via a short spacer including at least a sulphur atom. The synthesis of these compounds has been carried out from 2-F-butylethyl iodide or from the 2-F-alkylethyl mercaptans in the case of the F-hexyl and F-octyl tails. The mesomorphic properties have been characterized by polarized light microscopy and by differential thermal analysis showing the peculiar contribution of each of the spacers. The influence of the fluorinated chain and the shape of the connector on the stability of the mesophases has been investigated. The compounds with a thioether or a hemithioacetal spacer showed no mesomorphic properties, whereas the structures with a thioester spacer showed a very interesting enantiotropic behaviour of the smectic A type over a wide temperature range. Furthermore from the series exhibiting liquid crystalline behaviour, increasing the number of fluoromethylene units simultaneously increases both the melting and the clearing temperature. These mesomorphic properties within the fluorinated series are compared with those of their monocatenar hydrocarbon homologues.     

Forward scattering theory of electric-field-gradient-induced birefringence

We attempt to resolve the discrepancy between the Buckingham—Longuet-Higgins (BLH) and Imrie—Raab (IR) theories of linear birefringence induced in a gas of dipolar molecules by an electric field gradient. To this end we present a new calculation of the effect, based on forward scattering of a light beam incident on a thin lamina of gas molecules. We work to electric quadrupole—magnetic dipole order. The beam undergoes a time delay which is proportional to the thickness of the lamina and the electric field gradient, and can therefore be interpreted in terms of a contribution to the refractive index of the gas due to the field gradient. The birefringence is obtained by considering appropriate polarizations of the incident beam. To avoid the occurrence of a divergent quantity, such as appears in the BLH theory, it is essential to take account of the finite beam width. Calculations are performed using both primitive (traced) and traceless molecular quadrupole moments; as required on basic grounds, these results are equivalent. They are also identical to the BLH result. By contrast, the IR result is physically unacceptable because it is not invariant with respect to the use of traced and traceless moments. The source of error in the IR theory remains unclear.     

On the theory of the Buckingham effect

We apply general arguments (based on spatial transformation properties, intrinsic symmetry and dimensional analysis) to the theory of the Buckingham effect (electric-field–gradient-induced birefringence in a gas). These yield, in a simple manner, the temperature-dependent and temperature-independent terms in the birefringence (each to within a numerical factor), and also the expression, derived by Buckingham and Longuet-Higgins, for the effective quadrupole centre of a molecule. We show in addition how the calculation of the two numerical factors can be simplified in our approach.     

ELLIPSOMETRY OF BLACK LIPID MEMBRANES OF EGG LECITHIN AND CHLOROPLAST EXTRACTS

Abstract— Ellipsometric angles and reflectivity of black lipid membranes containing either egg lecithin or chloroplast extracts were measured at a wavelength of 6328 Å. Evidence was found for positive uniaxial anisotropy in membranes of lecithin. If the thickness of those films is assumed to be 62 Å, the refractive index normal to the film surface is 1.471 ± 0.004, and the refractive index parallel to the film surface is 1.454 ± 0.003. The results for membranes of chloroplast extracts also indicate a positive anisotropy in the indices of absorption.