Structure, 31P and 13C chemical shift anisotrophy of (CH3)3P, (CH3)3PO, (CH3)3PS and (CH3)3PSe as determined by liquid crystal NMR spectroscopy

The ¹³P and ¹³C spectra of the triply ¹³C labelled molecules (CH₃)₃P, (CH₃)₃PO, (CH₃)₃PS and (CH₃)₃PSe oriented in a nematic phase are reported. The CPC bond angles have been measured. The ¹³P chemical shift tensor shows a large anisotropy except in the case of (CH₃)₃P. The abnormal large value observed for the PSe bond length suggests a large anisotropy of the ¹J(PSe) spin coupling.     

Cationic polymerization of p-substituted α-methylstyrenes. III. Effect of polymerization conditions on tacticity and molecular weight for p-chloro-α-methylstyrene

The cationic polymerization of p-chloro-α-methylstyrene was investigated for the effect of initiator and solvent on polymer tacticity, molecular weight, and molecular weight distribution. The products were generally crystalline polymers of 80–90% syndiotactic content with fairly high molecular weights and broad molecular weight distributions. Tacticities and molecular weight distributions followed similar patterns suggesting that the effect of reaction conditions on ionpair end-group structures was the dominant factor.     

The electronic structure of heteroaromatic molecules; ab initio calculations and photoelectron spectra for the isomeric-oxazoles and some -oxadiazoles

The UV photoelectron spectra are reported for isoxazole and 1,3,4-oxadiazole (He(I) region), oxazole and 1,2,5-oxadiazole (He(I) and He(II) regions). Marked fine structure is apparent on some of the spectra. The spectra have been assigned on the basis of ab initio calculations, and by comparison with the azoles and thiazoles. Variations in the lone pairs levels at O-, S- and N- across the azoles, oxazoles, thiazoles and azines are discussed. It is suggested that “through-bond” interactions are more widespread in the azines than previously noted.     

Torsional eigenvalues of the water trimer on several ab initio potential surfaces

Eigenvalues corresponding to the three torsional degrees of freedom were calculated for the water trimer and its deuterated isotopomer in four sets of calculations involving different potential energy surfaces. The four potential surfaces were developed in this work by reparametrization of the CKL function against four sets of ab initio energies calculated with and without counterpoise correction. Transition frequencies corresponding to the low-frequency torsional motions of the trimer were calculated and then compared with those found from experiment to assess the accuracy of each potential energy surface. Although reparametrization of the CKL function to a set of counterpoise-corrected energies yielded transition energies that are in qualitative agreement with those from experiment, reparametrization to another set of counterpoise-corrected energies resulted in highly inaccurate values of the transition energy. As a consequence, our results demonstrate that caution must be exercised in the implementation of the counterpoise method as it does not always lead to more accurate ab initio calculations. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 233–252, 1998     

Nucleotides. Part XLIV. Synthesis,characterization, and biological activity of monomeric and trimeric cordycepin-cholesterol conjugates and inhibition of HIV-1 replication

The antivirally active 3′-deoxyadenylyl-(2′–5′)-3′-deoxyadenylyl-(2′–5′)-3′-deoxyadenosine (cordycepin trimer core) was modified at the 2′- or 5′-terminus, by attachment of cholesterol via a carbonate bond (→ 15 ) or a succinate linker (→ 16 and 27 ) to improve cell permeability. The corresponding monomeric conjugates 4 , 7 , and 21 of cordycepin were prepared as model substances to study the applicability of the anticipated protecting groups – the monomethoxytrityl (MeOTr), the (tert-butyl)dimethylsilyl (tbds), and the β -eliminating 2-(4-nitrophenyl)ethyl (npe) and 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) groups – for the final deblocking steps without harming the ester bonds of the conjugate trimers. The syntheses were performed in solution using phosphoramidite chemistry. The fully protected trimer conjugates 13 , 14 , and 26 as well as all intermediates were characterized by elemental analyses, UV and ¹H-NMR spectra. The deblocked conjugates 15 , 16 , and 27 were pure according to HPLC and showed the correct compositions by mass spectra. Comparative biological studies indicated that cordycepincholesterol conjugate trimers 16 and 27 were 333- and 1000-fold, respectively, more potent inhibitors of HIV-1-induced syncytia formation than cordycepin trimer core.     

Monitoring of liquid-phase organic reactions by photoelectron spectroscopy

There are strings attached: after linking the reacting groups to head groups of ionic liquids to drastically lower the vapour pressures of the reactants, ordinary liquid-phase organic reactions can be monitored by in situ X-ray photoelectron spectroscopy. This approach is demonstrated for the nucleophilic substitution of an alkyl amine and an alkyl chloride moiety, which are attached to the cation and anion of ionic liquids, respectively.     

Configuration-selective spectroscopic studies of Er3+ centers in ErSc2N@C80 and Er2ScN@C80 fullerenes

Low temperature photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopy of high purity ErSc(2)N@C(80) and Er(2)ScN@C(80) fullerenes reveal at least two metastable configurations of the Er(3+) ion within the cage, consistent with previous observations from x-ray diffraction. Using PLE measurements at a number of different emission wavelengths we have characterized the ground state, (4)I(152), and the first excited state, (4)I(132), of the various Er(3+) configurations and their crystal-field splitting. We present detailed energy level diagrams for the ground and excited states of the two dominant configurations of ErSc(2)N@C(80) and Er(2)ScN@C(80).     

A conductance investigation of HCl in aqueous solutions of tetrahydrofuran,dimethoxyethane and dioxane

Conductance of dilute solutions of HCl in water-tetrahydrofuran (THF), water-dioxane and water-dimethoxyethane (DME) were measured and the data processed using the Justice-Ebeling equation to evaluate the limiting conductance _O, the association constant K_A and the apparent distance of closest approach a'. The Friedman-Rasaiah Gurney cosphere overlap term d_+–/kT was calculated from a' values and illustrates the different solvation pattern of dioxane compared to that found for THF and DME. It would appear that dioxane can solvate cations more strongly due to its ability to form a boat configuration around a cation. The association constants are reasonably reproduced by the Bjerrum equation using realistic molecular dimensions of the ions involved for the distance of closest approach. The limiting conductance in the mixtures illustrates clearly the different mechanism for proton conductance compared to that for the cesium ion. The dielectric constants, viscosities and densities of the solvent mixtures were measured and are reported. The lowest dielectric constant for each type of solvent mixture was about 10.     

Anionic polymerization with expansion in volume

New bicyclic and tricyclic compounds have been synthesized by the Lewis acid-catalyzed condensation of epoxides with cyclic acid anhydrides or cyclic bislactones. These materials take part in the anionic addition polymerization of amine-functional polyamides with diepoxides, and modify the shrinkage that is characteristic of the reaction. It is possible to control the extent of shrinkage by choosing an appropriate comonomer and by adjusting the concentration of this material in the reaction mixture.