Synthesis of stable and cell-type selective analogues of cyclic ADP-ribose, a Ca(2+)-mobilizing second messenger. Structure--activity relationship of the N1-ribose moiety

We previously developed cyclic ADP-carbocyclic ribose (cADPcR, 2) as a stable mimic of cyclic ADP-ribose (cADPR, 1), a Ca(2+)-mobilizing second messenger. A series of the N1-ribose modified cADPcR analogues, designed as novel stable mimics of cADPR, which were the 2"-deoxy analogue 3, the 3"-deoxy analogue 4, the 3"-deoxy-2"-O-(methoxymethyl) analogue 5, the 3"-O-methyl analogue 6, the 2",3"-dideoxy analogue 7, and the 2",3"-dideoxydidehydro analogue 8, were successfully synthesized using the key intramolecular condensation reaction with phenylthiophosphate-type substrates. We investigated the conformations of these analogues and of cADPR and found that steric repulsion between both the adenine and N9-ribose moieties and between the adenine and N1-ribose moieties was a determinant of the conformation. The Ca(2+)-mobilizing effects were evaluated systematically using three different biological systems, i.e., sea urchin eggs, NG108-15 neuronal cells, and Jurkat T-lymphocytes. The relative potency of Ca(2+)-mobilization by these cADPR analogues varies depending on the cell-type used: e.g., 3"-deoxy-cADPcR (4) > cADPcR (2) > cADPR (1) in sea urchin eggs; cADPR (1) > cADPcR (2) approximately 3"-deoxy-cADPcR (4) in T-cells; and cADPcR (2) > cADPR (1) > 3"-deoxy-cADPcR (4) in neuronal cells, respectively. These indicated that the target proteins and/or the mechanism of action of cADPR in sea urchin eggs, T-cells, and neuronal cells are different. Thus, this study represents an entry to cell-type selective cADPR analogues, which can be used as biological tools and/or novel drug leads.     

Dewetting of liquids on ceramic surfaces at high temperatures.

The influence of surface structure and chemistry on high-temperature dewetting of silicate liquids on ceramic surfaces has been investigated. Model systems based on well-defined crystallography and known chemistry have been used to illustrate the effect of surface roughness and chemistry on the dewetting process. Reconstructed ceramic surfaces provide ideal substrates to study effects of surface roughness. It has been shown that the morphology of dewet droplets depend on the length scale and the crystallography of the facets on the surface. Complex pattern formation due to solute redistribution during dewetting is illustrated in the case of SiO2 dewetting on (001) rutile substrates. The role of kinetics on the dewetting process has also been clarified.     

Some jacobi matrices with decaying potential and dense point spectrum

We discuss doubly infinite matrices of the formM _ij= _i,j+1+ _i,j–1+V _{i ij} as operators on ². We present for each >0, examples of potentialsV _n with |V _n|=O(n ^–1/2+) and whereM has only point spectrum. Our discussion should be viewed as a remark on the recent work of Delyon, Kunz, and Souillard.Research partially supported by USNSF under grant MCS 81-20833     

Transference numbers for ultra concentrated solutions of aqueous hydrochloric acid at 25°C

Transference numbers of HCl(aq) solutions at 25°C, from 0.01 to 13.6 mol-kg^–1(m) have been obtained by measuring the emf of cells with transference using hydrogen gas/platinum electrodes. Good agreement is obtained at concentrations up to 1 m with all previous data, and our results strongly corroborate those of King and Spiro over the 2–8m concentration range. The transference numbers of the hydronium ion fit the empirical equation, _H ^HCl = 0.821 + 0.0457m ^1/2 – 2.476×10^–2m – 1.90×10^–4 m ² – 1.45×10^–5 m ³ the maximum deviation in T _H ^HCl being 0.003.     

Effect of low amounts of cholesterol on the swelling behavior of floating bilayers

The effect of the addition of 1, 2, 4, and 6 mol % cholesterol to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) floating bilayers has been investigated by neutron reflectivity. All samples exhibited fully stable and reversible gel and fluid phases. Around the main lipid phase transition temperature, DPPC double bilayers exhibit large increases in the water layer separating the bilayers and the upper bilayer roughness. The inclusion of low amounts of cholesterol reduced the swelling of the water layer between the bilayers and the upper bilayer roughness and progressively widened the temperature range over which swelling occurs. Results from asymmetric bilayers are also reported. A higher amount of cholesterol in the lower bilayer induces a smaller swelling of the water layer between the bilayers than in the symmetric case. Finally, the effect of the inclusion of a leaflet of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) was investigated. The presence of a leaflet with a higher gel-transition temperature (T(m)) modifies the phase behavior of the lower T(m) leaflet.     

Long-Range 31P-31P Spin Coupling Constants in the 31P NMR Spectra of Phosphite Triesters

Abstract

Data are presented on the magnitudes of ⁵ J _pp and ⁶ J _PP spin-spin coupling constants in the ³¹P NMR spectra of a variety of novel polyphosphite triesters.     

Modelling interaction between ammonia and nitric oxide molecules and aquaporins

Aquaporin is a family of small membrane-proteins that are capable of transporting nano-sized materials. In the present paper, we investigate the structure of these channels and provide information about the mechanism of individual molecules being encapsulated into aquaglyceroporin (GlpF) and aquaporin-1 (AQP1) channels by calculating the potential energy. In particular, we presents a mathematical model to determine the total potential energy for the interaction of the ammonia and nitric oxide molecules and different aquaporin channels which we assume to have a symmetrical cylindrical structure. We propose to describe these interactions in two steps. Firstly, we model the nitrogen atom as a discrete point and secondly, we model the three hydrogen atoms on the surface of a sphere of a certain radius. Then, we find the total potential energy by summing these interactions. Next, by considering the nitric oxide molecule as two discrete atoms uniformly distributed interacting with GlpF and AQP1 channels then gathering all pairs of interaction to determine the potential energy. Our results show that the ammonia and nitric oxide molecules can be encapsulated into both GlpF and AQP1 channels.