The Impact of the Phenyl Spacer on the Electronic Structure and Spectra of Porphyrin Dimers

Quantum-chemical investigation of the electronic structure and properties of the excited states of porphyrin dimers, in which monomeric subunits are linked by the phenyl spacer, is performed by semiempirical methods. The molecular orbitals of the monomeric subunits are shown to interact with each other via molecular orbitals of the phenyl ring. Comparison of the experimental absorption data and quantum-chemical calculations of electronic absorption spectra for different conformations of Zn-tetraphenylporphyrin dimer is performed and the main conformation of the dimer in a solution at 295 K, in which the planes of tetrapyrrole macrocycles are located at an angle of about 60°, is substantiated.     

α-Particle Loss from Cylindrical Magnetized DT Plasma

-particles from fusion reactions in a DT magnetized plasma are confined inside the plasma not only by magnetic fields but also by induced electric fields which are due to the different mobilities of -particles and electrons. Criteria are derived for the -confinement in a cylindrical plasma, inertially confined by a heavy liner. It is observed that the suprathermal population in the DT plasma will influence the overall dynamics.     

The Order Parameter and Phase Transformations in Compounds with Ionic Stoichiometry

The paper considers instability of a symmetric linear ion chain against a spontaneous distortion that orders ions of opposite charge without a multiple change in the spacing. Transverse deformation in dense chains is observed. The dipolar interaction responsible for 3D ordering of similar structures of Cu—O chains in yttrium perovskites has been assessed. The superclose ion packing in Cu—O chains is explained by the existence of an oriented hole orbital in the electronic structure of bivalent copper. The possible role of this orbital as an additional degree of freedom leading to thermodynamic singularities at intermediate temperatures below the tetra–ortho transition temperature has been investigated.     

New MnO–Nb(Ta)2O5 Phases Produced at High Pressures and Temperatures

Phase formation at high pressures and temperatures were studied in the MnO–Nb(Ta)₂O₅ system. New rhombohedral modifications of Mn₄Nb₂O₉ and Mn₄Ta₂O₉, two new modifications of MnTa₂O₆, and two modifications of Mn₂Ta₂O₇ were obtained. They were structurally identified.     

A Biokinetic Model to Describe Consequences of Inhibition/Stimulation in <Emphasis Type="Italic">DNA</Emphasis>-Proofreading and -Repair,Part 4

Summary. In previous papers a strongly simplified physical-mathematical (biokinetic) model has been presented, which dealt with the factors influencing the timely development of DNA mismatches dependent cells (malignant cells) in their kinetic competition to the development of normal somatic cells (i.e. cells with correct genetic information). The kinetic results have been studied by comparing them with experimental results reported in the literature upon inhibiting the organisms own enzymatic DNA-proofreading and repair machinery. In spite of the fact that the model uses fully the chances of kinetics, which allows to describe even rather complicated systems with many regulation circuits and feed back loops in a rather simple, summarizing way, it has been demonstrated that the model does not only well describe the experimentally found significant increases of mutants in cases when the DNA repair system has been inhibited, but it can also reflect cancer-development and the efficacy of classical cancer therapies like surgery or chemotherapy as well.In applying the predictions of the model as to the opposite of an inhibition of the DNA repair system, i.e., in testing the results, if the organisms own repair systems were stimulated, the model shows that there could be a chance for a new, adjuvant cancer-therapy if this concept was combined with biochemical facts and clinical findings which are reported in the literature.In continuation of this concept, the predictions of the model have been compared with findings upon cancer-therapies by apoptosis-triggerers like tamoxifen. Further, according to the fact that there exists literature by which it is demonstrated by clinical facts that it is not necessary to use living cells (e.g. from umbilical cords blood or bone-marrow) to achieve surprising therapeutic successes in cancer therapy, but also cell-free human-placenta-extracts (HPEs) can be similarily effective, it has been tried in a first preliminary analytical effort to characterize effector-substances contained therein.Received January 27, 2003; accepted (revised) March 25, 2003 Published online August 18, 2003     

A Complete Solution to a Conjecture on the β-Polynomials of Graphs

In 1990, Gutman and Mizoguchi conjectured that all roots of the -polynomial (G,C,x) of a graph G are real. Since then, there has been some literature intending to solve this conjecture. However, in all existing literature, only classes of graphs were found to show that the conjecture is true; for example, monocyclic graphs, bicyclic graphs, graphs such that no two circuits share a common edge, graphs without 3-matchings, etc, supporting the conjecture in some sense. Yet, no complete solution has been given. In this paper, we show that the conjecture is true for all graphs, and therefore completely solve this conjecture.     

Evidence of Ternary Inclusion Complexes Formation Using Factorial Design and Determination of Their Formation Constant

Evidence of the interaction among the [PbAc]⁺ and[PbEDTA]^-2 with the -cyclodextrin (-CD)is shown, using a 2⁴ factorial design. The factors used werethe [Pb(II)], [-CD], [Ac^-] and [EDTA] concentrationsat pH = 6.2. The statistical results indicate that the changes inchemical response for these species are associated to theinteraction among these factors. Spectrophotometric andelectrochemical studies were undertaken to assess the interactions.The equilibrium constants for inclusion complexes were determinedFor -CD-[PbAc]⁺ and -CD-[PbEDTA]^-2.     

Electron density investigation of a push-pull ethylene (C14H24N2O2.H2O) by X-ray diffraction at T = 21 K

The electron charge distribution in a strongly twisted push-pull ethylene [PPE, 3-(1,3-diisopropyl-2-imidazolidinylidene)-2,4-pentanedione] has been determined by low temperature (T = 21 K) single-crystal X-ray diffraction analysis. The derived electronic properties are consistent with a zwitterionic molecule, as indicated by a charge transfer of 0.82(16) e from the push to the pull moieties and a charge polarization of 0.29(7) e on the olefinic bond. A dipole moment of 12(3) D has been determined, which compares well with ab initio theoretical results in terms of both modulus and orientation. The second moments, which have also been obtained with good precision, characterize PPE as a highly quadrupolar molecule. The special electronic features of the molecule confer particular topological properties to the electron density distribution, as evidenced by comparison with "standard" organic molecules. The crystallographic asymmetric unit of the present system includes one water molecule, which is hydrogen bonded to PPE. Its topological properties have also been investigated, together with an analysis of the hydrogen bonds involved.     

tert-Butylphosphonic acid: from the bulk to the gas phase

The structure of tert-butylphosphonic acid in the solid, in solution, and in the gas phase was studied by single-crystal X-ray diffraction, (1)H and (31)P NMR spectroscopic studies in solution, solid-state (31)P NMR spectroscopy, and electrospray ionization mass spectrometry. In addition, density functional theory (DFT) calculations at the B3LYP/6-31G*, B3LYP/6-31+G*, and B3LYP/6-311+G* level of theory for a large number of H-bonded aggregates of the type (tBuPO(3)H(2))(n) (C(n), P(n); n=1-7) support the experimental work. Crystallization of tBuPO(3)H(2) from polar solvents such as CH(3)CN or THF gives the H-bonded one-dimensional polymer 2, whereas crystallization from the less polar solvent CDCl(3) favors the formation of the H-bonded cluster (tBuPO(3)H(2))(6).CDCl(3) (1). In CDCl(3) the hexamer (tBuPO(3)H(2))(6) (C(6)) is replaced by smaller aggregates down to the monomer with decreasing concentration. DFT calculations and natural bond orbital (NBO) analyses for the clusters C(1)-C(7) and the linear arrays P(1)-P(7) reveal the hexamer C(6) to be the energetically favored structure resulting from cooperative strengthening of the hydrogen bonds in the H-bonded framework. However, the average hydrogen bond strengths calculated for C(6) and P(2) do not differ significantly (42-43 kJ mol(-1)). The average distances r(O.O), r(Obond;H), r(Pdbond;O), and r(Pbond;OH) in C(1)-C(7) and P(1)-P(7) are closely related to the hydrogen bond strength. Electrospray ionization mass spectrometry shows the presence of different anionic species of the type [(tBuPO(3)H(2))(n)-H](-) (A(1)-A(7), n=1-7) depending on the instrumental conditions. DFT calculations at the B3LYP/6-31G* level of theory were carried out for A(1)-A(6). We suggest the dimer [(tBuPO(3)H(2))(2)-H](-) (A(2)) and the trimer [(tBuPO(3)H(2))(3)-H](-) (A(3)) are the energetically favored anionic structures. A hydrogen bond energy of approximately 83 kJ mol(-1) was calculated for A(2). Electrospray ionization mass spectrometry is not suitable to study the assembling process of neutral H-bonded tert-butylphosphonic acid since the removal of a proton from the neutral aggregates has a large influence on the hydrogen bond strength and the cluster structure.     

Asymmetric reduction of acetophenone and propiophenone by NaAl(IPTOLate)H2 combined with enantiomeric enrichment of the reaction product as an inclusion complex with IPTOL

An improved procedure was developed for asymmetric reduction of acetophenone and propiophenone by the chiral reagent NaAl(IPTOLate)H₂. This procedure is based on isolation of the chiral alcohol that formed as a crystalline host—guest complex with the IPTOL ligand. The enantiomeric enrichment of the product was as high as 97% ee. The ability of IPTOL and its analogs to form host—guest complexes with a number of ether-type solvents, 1-phenylethanol, and 1-phenylpropan-1-ol as well as thermal stabilities of IPTOL-containing complexes with these alcohols were studied.