Fragmentation during the formic acid/formaldehyde (eschweiler-clarke) methylation of polyamines

Eschweiler-Clarke methylations of both acyclic and cyclic polyamines can lead to methylation products of fragments of the original polyamine; thus 1,5,9,13-tetra-azatridecane yields 1,1,3,3-tetramethylpropanediamine exclusively and 1,5,9-triazacyclododecane gives 45% 1,5,9-trimethyl-1,5,9-triazacyclodecane and 45% 2,6,10-trimethyl-2,6,10-triazaundecane.     

Magnetic structures and crystal field in the heavy electron materials YbAgGe and YbPtIn

We have examined the magnetic properties of the heavy electron compounds YbAgGe and YbPtIn by ¹⁷⁰Yb M?ssbauer spectroscopy down to 0.1 K, and the crystal field properties of YbAgGe by Perturbed Angular Correlations (PAC) measurements up to 900 K. In YbAgGe, we show that each of the two magnetically ordered phases below 0.8 K involves a specific incommensurate modulation of the Yb moment. An analysis of existing low temperature specific heat data suggests the persistence of fluctuations of the correlated Yb spins down to 0.1 K. The PAC data allow to discriminate among proposed Yb³⁺ crystal field level schemes. In YbPtIn, we show that the low temperature magnetic order phase has an antiferro-para structure, where zero moment Yb ions coexist with large moment ones, and that a 90° moment reorientation occurs at 1.4 K.     

Theoretical study of PO and PO−

The diatomic systems, PO and PO^– are studied, using numerical Hartree-Fock (NHF) and coupled-cluster calculations. The latter employs a hybrid NHF and Slater orbital basis set. Highly accurate CCSD methods predict bond lengths accurate to <0.004 Å and frequencies to 60 cm^–1. In addition the electron affinity of PO is computed to be 0.89 eV compared to an experimental value of 1.09±0.01. Comparisons are made with SCF and MBPT(2) results for PO⁺ using conventional basis sets.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayGuggenheim Fellow     

Structural and rate studies of the 1,2-additions of lithium phenylacetylide to lithiated quinazolinones: influence of mixed aggregates on the reaction mechanism

The 1,2-addition of lithium phenylacetylide (PhCCLi) to quinazolinones was investigated using a combination of structural and rate studies. (6)Li, (13)C, and (19)F NMR spectroscopies show that deprotonation of quinazolinones and phenylacetylene in THF/pentane solutions with lithium hexamethyldisilazide affords a mixture of lithium quinazolinide/PhCCLi mixed dimer and mixed tetramer along with PhCCLi dimer. Although the mixed tetramer dominates at high mixed aggregate concentrations and low temperatures used for the structural studies, the mixed dimer is the dominant form at the low total mixed aggregate concentrations, high THF concentrations, and ambient temperatures used to investigate the 1,2-addition. Monitoring the reaction rates using (19)F NMR spectroscopy revealed a first-order dependence on mixed dimer, a zeroth-order dependence on THF, and a half-order dependence on the PhCCLi concentration. The rate law is consistent with the addition of a disolvated PhCCLi monomer to the mixed dimer. Investigation of the 1,2-addition of PhCCLi to an O-protected quinazolinone implicates reaction via trisolvated PhCCLi monomers.     

Ring size effects. III. Carbonium ion stability as a factor in the course of the pinacol rearrangement

The formation of the initial carbonium ion in the pinacol rearrangement will be the major factor in determining product composition when the reaction is carried out at 0°C with concentrated sulfuric acid.     

A graph-theoretic approach to quantitative structure—activity/reactivity studies

Characterization of molecular species based on the use of suitable graph invariants (graph paths, in particular) can provide a quantitative means of encoding structure; the technique is complementary to commoner approaches to studies of quantitative structure— activity relationships. Graph path encoding is here applied to quantitative studies of relationships between molecular structures and biological activity; the examples are the rates of various substrate reactions with hexoldnase, and the potential opiate-like activity of enkephalin analogs.     

Two-, three-, and four-coordinate Ag(I) coordination polymers formed by the novel phosphinite PPh2(3-OCH2C5H4N)

The novel phosphinite PPh(2)(3-OCH(2)C(5)H(4)N) (1) has been synthesized, and its coordination properties to Ag(I) have been studied. When reacted in a 1:1 ratio with Ag(I), coordination polymers with different coordination numbers about the Ag are found depending on the anion. For PPh(2)(3-OCH(2)C(5)H(4)N)AgBF(4) (2), a two-coordinate Ag is observed with a P-Ag-N angle of 167 degrees. Mixed three and four coordination about Ag is observed for PPh(2)(3-OCH(2)C(5)H(4)N)AgOTf (3), and for the trifluoroacetate derivative, PPh(2)(3-OCH(2)C(5)H(4)N)Agtfa (4), only a four-coordinate Ag is produced. X-ray crystal-structure determinations for compounds 2-4 have been carried out. The X-ray structures show a wide range of Ag-Ag distances in the polymers, which are dependent on the conformation of the bridging ligand.     

Singular value decomposition applied to the compression of T3 amplitude for the coupled cluster method

We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented.     

Effect on topical 5-methoxypsoralen on tumorigenesis induced in albino and pigmented hairless mouse skin by UV irradiation

A new line of the Skh:HRII hairless pigmented mouse (black juvenile coat) is described which has been selectively bred for the capacity to respond consistently to simulated solar UV radiation with a continuous and strong tan. This mouse demonstrates a degree of protection from chronic UV-induced tumorigenesis when compared with the Skh:HRI hairless albino mouse, and has been used here to study the effect of induced melanogenesis on phototumorigenesis. Mice were irradiated for 10 weeks with incremental doses of simulated solar UV radiation (UVA + B) from a fluorescent tube source which induced tumours in 100% of albino mice and 93% of black mice by 200 days (minimally oedemal), or with 60% of this dose (sub-oedemal) which induced tumours in 85% of albino mice and 65% of black mice. Mice were also exposed to the UVA component of these radiation sources, obtained by window glass filtration. The effect of topical 5-methoxypsoralen (5-MOP) was examined, at either 0.003% with minimally oedemal UVA + B or its UVA component alone, or at 0.01% with sub-oedemal UVA + B or its UVA component alone, in both albino and black mice. The 5-MOP concentrations were selected as the maximum concentration which did not increase the erythema and oedema responses after a single exposure to minimally oedemal or sub-oedemal UVA + B. At 200 days, the tumorigenic response to sub-oedemal UVA + B was significantly increased by topical 5-MOP, to 100% in albinos and 93% in black mice. In contrast, tumorigenesis in response to minimally oedemal UVA + B was unaffected by topical 5-MOP. The UVA component alone of either irradiation regime was not tumorigenic under these conditions. When combined with topical 5-MOP, the UVA of minimally oedemal UVA + B became moderately tumorigenic, and resulted in a tumour incidence of 23% in albinos and 14.5% in black mice. However, the UVA component of sub-oedemal UVA + B, when combined with topical 5-MOP, was highly tumorigenic specifically in albino mice, inducing tumours in 93% of albino mice but in only 27% of black mice. Tan intensity resulting from minimally oedemal UVA + B was not enhanced by topical 5-MOP, and its UVA component combined with 5-MOP resulted in only a minimal tan. However, the tan intensity resulting from sub-oedemal UVA + B with topical 5-MOP was strongly increased, although its UVA component combined with 5-MOP did not produce a perceptible tan.(ABSTRACT TRUNCATED AT 400 WORDS)