Properties of hydration shells of protein molecules at their pressure- and temperature-induced native-denatured transition.

Properties of water at the surface of biomolecules are important for their conformational stability. The behaviour of hydrating water at protein transition (t) pressures P(t) and temperatures T(t) , with the points (P(t),T(t) ) lying in the Native-Denatured (N-D) transition line, is studied. Hydration shells at the hydrophilic regions of protein molecules with surface charge density sigma are investigated with the help of the equation of state of water in an open system. The local values of sigma rather close to each other (sigma(D) approximately 0.3 C m(-2)) are found for six different experimental lines of the N-D transition found in the literature. The values sigma(D) correspond to the crossings of the total pressure (P(t)+Pi) vs sigma isotherms at different T(t) (Pi-electrostriction pressure). The pressures P(t) and temperatures T(t) appear to be related with some selected sites at the surfaces of the protein molecules.     

Crystal structure of 7-cyano-6,7-dimethyl-1-phenyl-1,3,6,7-tetrahydro-2,1-benzoxaphospole 1-oxide

The crystals (C₁₆H₁₈NO₂P,M _r=287.30) are orthorhombic, space group Pbca witha=8.200(2),b=14.857(2), andc=24.396(5)Å,V=2972.1 ų,Z=8,D _x=1.284 mg m^–3,(MoK)=0.71069 Å,=1.90 cm^–1,F(000)=216,T=295K. FinalR=0.044 for 1673 observed reflections collected on a diffractometer. Structure solved by direct methods.Cis-junction and double bond in the six-membered ring cause its almost ideal sofa conformation. The two neighboring methyl groups are cis, and cyano substituent is in an equatorial position. There is a shortintramolecular H(o-phenyl)O(endocyclic) contact of 2.53(3)Å and the phenyl ring is in a less favorable rotational orientation due to molecular packing.     

Conformational mobility in chemically-modified cyclodextrins

The observation that per-2,6-O-methyl-3-O-benzoyl--cyclodextrin (1) displays some unusual conformational behaviour in solution has led to a detailed investigation by (dynamic) NMR spectroscopy of the equilibration process that occurs in solutions of per-2,3-O-benzoyl--cyclodextrin (3) and some related compounds (7–9) between conformational isomers with averagedC ₆ andC ₃ molecular symmetries in certain organic solvents such as benzene, dichloromethane, and chloroform. The solvent dependence of the conformational equilibrium is also reflected in a spread of values for the specific optical rotations for 3 from +9° in 1,1,2,2-tetrachloroethane, where there is a degenerate equilibrium between species withC ₃ molecular symmetry, to +92° in acetone where a species with averagedC ₆ symmetry is present.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Equivalence of two series of spherical representations of a free group

Summary The spherical principal series of a non-commutative free group may be analytically continued to yield a series of uniformly bounded representations, much as the spherical representations (in1/2) + it of SL (2,R) may be analytically continued in the strip 0 < Rez < 1. This series of uniformly bounded representations was constructed and studied by A. M.Mantero and A.Zappa. Independently T.Pytlik and R.Szwarc introduced and studied representations of the free group which contain a series of subrepresentations indexed by spherical functions. Both series consist of irreducible representations and include the spherical complementary series. The aim of this paper is to prove that the non-unitary uniformly bounded representations of the two series are also equivalent.     

Eigenvibrations of the expanding universe

A theoretical interpretation of the observed periodicity of large-scale (128 Mpc) correlations of galaxies is proposed as due to eigenvibrations of the closed expanding universe. Eigensolutions of the equations of motion for a scalar field in an inflationary model allow one to compute the energy density, interpreted as matter density. Isotropic eigensolution give rise to a matter density distribution having a periodic structure centered at the north pole of the closed Robertson-Walker universe represented by S³/Z₂. It is able to reproduce well the striking periodicity of the observational data, in the galactic north-south directions. The dipole and quadrupole eigensolutions and the location of the co-moving observer in a point of S³/Z₂ different from the center of the vibrational structure would imply, in a theoretically well predictable way, a decrease of the observed periodicity in some other directions.Partially supported by the State Committee for Scientific Research, Grant No. 2-0206-91-01.     

A simple method for determining the multilayer effects in adsorption of alcohols on silica gel

The excess adsorption isotherms ofn-pentanol, pentan-2-ol and 2-methylbutan-2-ol from binary and ternary solutions in benzene andn-heptane were measured. Experimental adsorption data are discussed in terms of a multilayer model of the surface phase. The main assumption of this model is that the surface layers being near the solid surface contain the molecules of the preferentially adsorbed component only. The phase-exchange reaction of molecules between bulk phase and last surface layer has been taken into account.On the basis of this theory it has been established for the investigated systems that the surface phase contains three molecular layers. Simultaneously appropriate surface phase capacities were determined.

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Eine einfache Untersuchungsmethode für Mehrschicht-Effekte bei der Adsorption von Alkoholen an Kieselgel

Zusammenfassung Die Adsorptionsisothermen binärer und ternärer flüssiger Mischungen vonn-Pentanol, 2-Pentanol oder 2-Methyl-2-butanol in Benzol und/odern-Heptan wurden bezüglich Kieselgel gemessen. Die experimentellen Daten der Adsorption wurden mittels des Mehrschichts-Modells der Oberflächenphase diskutiert. Die Hauptvoraussetzung dieses Modells ist die Annahme, daß die Oberflächenschichten, die sich in der Nähe des Kieselgels befinden, nur Moleküle der bevorzugt adsorbierten Komponente enthalten. Es wurde auch die Phasen-Austauschreaktion von Molekülen zwischen Phaseninnerem und der letzten Oberflächenschicht in Betracht gezogen.Auf der Basis dieser Theorie wurde für die untersuchten Systeme festgestellt, daß die Oberflächenphase aus drei Molekülschichten besteht. Außerdem wurden die ermittelten Volumina der Oberflächenphase berechnet.

     

Hydrogen segregation on a palladium hydride surface

Surface phenomena occurring in the process of palladium hydride formation during the interaction of thin Pd film with molecular hydrogen were studied by means of simultaneous measurements of surface potential and H₂ pressure. This allows to differentiate between various states of the adsorbate, and to correlate their behaviour with hydrogen concentration on the surface and in the bulk. Two distinct states of the adsorbate were determined: (i) the negatively polarized, atomic adspecies, stable on the surface, arising at the beginning of the adsorption, referred to as β^-, and (ii) the induced, positively polarized, atomic adspecies, incorporating quickly from the surface into the bulk, referred to as β⁺. The β⁺ adspecies form a precursor surface state for PdH_x creation. It has been found that at low temperature (78K) the β⁺ adspecies are placed above the surface image plane (SIP). Under these conditions, the maximal hydrogen concentration on the palladium hydride surface approaches 2, while in the bulk the (H/Pd) ratio does not exceed 1. At higher temperatures (120K, 160K), when the β⁺ adspecies are located below the SIP, hydrogen concentration on the surface and in the bulk is uniform, approaching (H/Pd) ˜ 1.     

Potentiometric method for the determination of calcium in blood serum

A procedure for the determination of calcium in serum based on the complexation of calcium by a fixed amount of iminodiacetate at pH 9.6 with detection with a calcium-selective electrode is described. The effect of common concomitants was investigated; no interference was observed. When the procedure was tested on control sera, the bias was < 3% (6–8 replicate measurements); the relative standard deviation was < 5%.     

Reduction of finite exhausters

In this paper we introduce the notation of shadowing sets which is a generalization of the notion of separating sets to the family of more than two sets. We prove that \({\bigcap_{i\in I}A_{i}}\) is a shadowing set of the family \({\{A_{i}\}_{i\in I}}\) if and only if \({\sum_{i\in I}A_{i}=\bigvee_{i\in I}\sum_{k\in I\setminus \{i\}}A_{i} + \bigcap_{i\in I}A_{i}}\). It generalizes the theorem stating that \({A\cap B}\) is separating set for A and B if and only if \({A+B=A\cap B+A\vee B}\). In terms of shadowing sets, we give a criterion for an arbitrary upper exhauster to be an exhauster of sublinear function and a criterion for the minimality of finite upper exhausters. Finally we give an example of two different minimal upper exhausters of the same function, which answers a question posed by Vera Roshchina (J Convex Anal, to appear).     

A tandem Petasis-Ugi multi component condensation reaction: solution phase synthesis of six dimensional libraries

Amino acids with three points of diversity generated from the Petasis boronic acid-Mannich reaction can be used as one of the four components of the Ugi condensation to prepare six dimensional libraries of dipeptide amides.