A simple reliable approximation for isotropic intermolecular forces. A critical test using HH(3Σu+) as a model

A simple semi-empirical approximation for the exchange energy (E_x), coupled with a tractable representation of the Coulomb energy (E_C), has been found to yield very accurate results for the isotropic part of the interaction energy (E_int = E_x + E_C) between two closed shell systems. The expression for E_int is based on the knowledge of the first order Coulomb energy and the first three terms in the asymptotic long range expansion of the second order Coulomb energy for the interaction and contains but one adjustable parameter which occurs in E_x. The usefulness of this approach for evaluating E_int is tested critically by using the non-bonded H(1s)H(1s) (³Σ_u⁺) interaction as a model (accurate values of the total interaction energy, the exchange energy, and various orders of Coulomb energies, are available for a wide range of R for this system). The results obtained for both E_int and (dE_int/dR) are inremarkable agreement with the exact results of Kotos and Wolniewicz for R > 3 a_o. Since the law of corresponding states for inert gas pairs holds equally well for the HH(³Σ_u⁺) interaction, our analysis of this simple system yields valuable information on the reliability of the approach for other van der Waals dimers.     

EVALUATION OF NEW BENZOPORPHYRIN DERIVATIVES WITH ENHANCED PDT EFFICACY*

Abstract— A first report on the biological evaluation of a series of isomerically pure benzoporphyrin derivatives ( cis- and frarcs-isomers) as methyl esters is described. In preliminary in vivo studies, the n- bexyl ether analogues of both cis- and trans -isomers of benzoporphyrin derivatives were found to be more active than the industrially prepared benzoporphyrin derivative, a mixture of monocarboxylic acids (BPDMA, Quadralogic Technologies, Vancouver). Further studies with 4-de-vinyl-4-(I-hexyloxyethyl) benzoporphyrin derivative showed that, like BPDMA, it had reduced residual skin phototoxicity compared in mice with Photofrin®. The uptake and clearance characteristics of BPDMA were also compared with the 4-(1-hexyloxyethyl)-derivative by in vivo reflection spectroscopy.     

Isomeric Schiff bases related by dual imino‐group reversals

Two isomeric pairs of Schiff bases, N,N′‐bis­(2‐methoxy­benzyl­idene)‐p‐phenyl­enediamine, C₂₂H₂₀N₂O₂, (I), and 2,2′‐dimeth­oxy‐N,N‐(p‐phenyl­enedimethyl­ene)dianiline, C₂₂H₂₀N₂O₂, (II), and (E,E)‐1,4‐bis­(3‐iodo­phen­yl)‐2,3‐diaza­buta‐1,3‐diene (alternative name: 3‐iodo­benzaldehyde azine), C₁₄H₁₀I₂N₂, (III), and N,N′‐bis­(3‐iodo­phen­yl)ethylenedi­imine, C₁₄H₁₀I₂N₂ [JAYFEV; Cho, Moore & Wilson (2005). Acta Cryst. E 61 , o3773–o3774], differ pairwise only in the orientation of their imino linkages and in all four individual cases occupy inversion centers in the crystal, yet all four compounds are found to assume unique packing arrangements. Compounds (I) and (II) differ substantially in mol­ecular conformation, possessing angles between their ring planes of 12.10 (15) and 46.29 (9)°, respectively. Compound (III) and JAYFEV are similar to each other in conformation, with angles between their imino linkages and benzene rings of 11.57 (15) and 7.4 (3)°, respectively. The crystal structures are distinguished from each other by different packing motifs involving the functional groups. Inter­molecular contacts between meth­oxy groups define an R₂²(6) motif in (I) but a C(3) motif in (II). Inter­molecular contacts are of the I⋯I type in (III), but they are of the N⋯I type in JAYFEV.     

Triphenylphosphonium-alloxan betaines

Alloxan and 1,3-dimethylalloxan react with triarylphosphines to generate zwitterionic adducts involving the phosphorus and the C-5 carbonyl oxygen atoms of alloxan. The adducts, unlike alloxan, did not induce permanent hyperglycemia but one analog did effect a transient rise in blood glucose.     

Bile acids LXIX. Selective K-Selectride reduction of 3,7-diketo steroids

The K-Selectride reduction at low temperature (-45°C) of 7-oxo-5α-holestan-3β-yl acetate and methyl 7-oxo-3α-hydroxy-5(β-cholanoate resulted in almost quantitative yield of the 7α-alcohol in the 5α-compound but only moderate yield of the 5β-analog. The simultaneous reduction of two carbonyl groups in the 3 and 7 positions afforded good to excellent yields of the diaxial diol in planar steroids (methyl 3,7-dioxo-5α-cholanoate, 3,7-dioxo-5α-cholestane and methyl 3,7-dioxo-5α-cholestan-27-oate) and only 14% of 3α,7α-(OH)₂ from methyl 3,7-dioxo-5β-cholanoate.     

Electropolymerization of aminophthalic acids. I. Polymerization of 4-aminophthalic acid

4-Aminophthalic acid has been polymerized in almost quantitative yield to low molecular weight polymer by electrochemical initiation at a platinum anode. Systems involving the acid, amine salt, and the ammonium salt have been explored; the acid and/or the amine salt of the acid provides the best means of obtaining polymer. Maximum molecular weight is attained in a very short time at low current densities (～2 hr at 50 mA). Thermogravimetric data indicate a temperature stability comparable to polyamide-imide polymers (400°C). Long reaction times and high current densities decrease molecular weight and polymer yield.     

Reactivity ratios for copolymerization of vinyl chloride with 2-methylpentyl vinyl brassylate by computerized linearization

A computerized version of the Fineman-Ross linearization procedure was used to determine reactivity ratios for copolymerization of vinyl chloride (monomer 1) and 2-methylpentyl vinyl brassylate (monomer 2). From differential refractometry data for the products of low-conversion copolymerization, the procedure gave r₁ = 1.06 and r₂ = 0.234. The ratios computed from chlorine contents of the same products were r₁ = 1.10 and r₂ = 0.239. The polarity factor (e₂) and general monomer reactivity (Q₂) calculated for monomer 2 from these ratios were, respectively, ?0.95 to ?0.98 and 0.032–0.033. The interquartile range for the copolymerization of a mixture of 60% monomer 1 and 40% monomer 2 was 1.4%. These values suggest that from suitable proportions of reactants, sufficiently homogeneous distribution of monomers can be achieved in copolymers of vinyl chloride and 2-methylpentyl vinyl brassylate to offer the possibility of effective internal plasticization.     

Polymerizable siloxane precursors having in-chain perfluoroalkyl groups

The synthesis and polymerization of several silphenylene siloxane polymer precursors containing a perfluoroalkylsegment in the backbone was carried out. The molecular weight characteristics of polymers from 1,3-bis[p(-hydroxydimethylsilyl)phenyl]hexafluoropropane and 1,3-bis[p(-dimethylaminodimethylsilyl)phenyl]hexafluoropropane were studied as a function of polymerization conditions. Polymers containing the dodecafluorohexane chain segment were also prepared. Polymers having inherent viscosities of 0.55 to 0.9 were obtained. The polymers crosslinked at room temperature to thermoset elastomers which were characterized by improved thermal and oxidative stability over dimethylsilicones. Room temperature swelling of the experimental polymers hydrocarbon solvents was also much lower than that of dimethylsilicones. The polymers containing the (CF₂)₃ and (CF₂)₆ linkages had glass transition points of ?12°C and ?34°C, respectively.     

Gödel axiom mappings in special relativity and quantum-electromagnetic theory

Exponential mappings into an imaginary space or number field for the axioms of a theory, which are in the form of propositional constants and variables, make possible: (a) an understanding of the meaning and differences between the Lorentz transformation constants, such that their product is still equal to one, but the axioms at each end of the transformations are logically inverse and separately consistent; (b) an interpretation of the psi function phase factor which is part of the axiomE=hf; (c) the unification of the quantum-mechanical psi function and the electromagnetic wave function. Thus, those statements whose mechanisms are unknown (the axioms of the theory) are to be assigned the axiom propositional number symbol and are to be associated with the complex probability eⁱ, which is a uniform factor of the energy equations expressing the physical state. Such probabilistic axiom functions can be associated with both the special theory of relativity and the quantum-electromagnetic theory.     

New information-theoretic foundations for quantum statistics

When the state of a physical system is not fully determined by available data, it should be possible nevertheless to make a systematic guess concerning the unknown state by applying the principles of information theory. The resulting theoretical blend of informational and mechanical constructs should then constitute a modern structure for statistical physics. Such a program has been attempted by a number of authors, most notably Jaynes, with seeming success. However, we demonstrated in a recent publication that the standard list of so-called mutually exclusive and exhaustive quantum states that is commonly employed by these authors is in fact not exhaustive. It follows that the information-theoretic foundations of quantum statistics must be reformulated. The present paper discusses the fundamental problems involved and establishes a format for the correct application of information theory to quantum mechanical situations.Work supported by a grant from Research Corporation.