Activities induced in the human body by thermal neutrons

Activities of 17 radionuclides, induced in the human body by the activation of 14 elements with thermal neutrons, were calculated. Resulting dependences of these activities on the activation time are shown in graphs.     

Semiempirical studies of core-electron binding energy shifts

The inner-core binding-energy shifts (BEs) of boron and carbon atoms in various chemical environments were studied by the semiempirical Self-Consistent Charge Molecular Orbital (SCC MO) method. The calculations are based on the initial ground state electrostatic potential model. The main feature of our approach is the empirical treatment of the coefficient relating BEs with the orbital populations of the host atom and the Madelung energy term. These adjustable parameters absorb a large portion of relaxation energy. The so obtained results are in good agreement with experimental data. They are better than earlier CNDO/2 results obtained by using either ground state or relaxation potential models. Present results indicate that semiempirical methods like SCC MO are able to account for changes in BE(1s) with a fair accuracy although the inner-shell electrons are not explicitly considered in the actual calculations.     

The proton affinity of the superbase 1,8-bis(tetramethylguanidino)naphthalene (TMGN) and some related compounds: a theoretical study

The spatial and electronic structure of the very strong neutral organic bases bis(tetramethylguanidino)naphthalene (TMGN), 4,5-bis(tetramethylguanidino)fluorene (TMGF) and some related compounds are explored by ab initio computational methods. Their affinity towards the proton is scrutinized both in the gas phase and in solution in acetonitrile. The protonation at the most basic center (the imine nitrogen) yields asymmetric and relatively strong intramolecular hydrogen bonds (IHB). It is found that the angular strain effect and steric repulsion practically vanish in TMGN which implies that its high absolute proton affinity (APA) has its origin in the inherent basicity of the guanidine fragment and a relatively strong IHB in [TMGN]H(+). The nonbonded repulsions in TMGF are higher than in TMGN, which in conjunction with a slightly stronger IHB in the corresponding conjugate acid makes it more basic: APA(TMGF)>APA(TMGN). An interesting new phenomenon is observed in both TMGN and TMGF: the proton triggers the resonance stabilization not only in the directly bonded guanidine moiety, but also in the other guanidine fragment which is more distant from the proton, albeit in a less pronounced manner. The latter feature is termed a partial protonation. This supports the hydrogen bonding and contributes to the IHB stabilization. Convincing evidence is presented that the solvent effect in acetonitrile is determined by two antagonistic factors: 1) the intrinsic (gas phase) proton affinity and 2) the size effect which is given by the ratio between the positive charge in molecular cation (conjugate acid) and the magnitude of the molecular surface. The resulting pK(a) values are given by an interplay of these factors.     

Preparation of samples of airborne particles for determination of metals

Summary A Soxhlet extraction procedure for the preparation of samples of airborne particulate matter for analysis by atomic-absorption spectrophotometry has been developed and tested by addition of known amounts of lead, iron, manganese, copper and cadmium and by analysing portions of atmospheric samples processed by (1) Soxhlet extraction, (2) acid digestion and (3) autoclave digestion. Soxhlet extraction proved to be superior to the other two procedures. It is simple and reliable, and offers less possibility of contamination by, or loss of, trace metals.

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Probengewinnung von Schwebstaub zur Metallbestimmung

Zusammenfassung Ein Verfahren der Soxhlet-Extraktion zur Probengewinnung für die Analyse von Luftverunreinigungsteilchen durch Atomarabsorption wurde ausgearbeitet und durch Zusatz bekannter Mengen Blei, Eisen, Mangan, Kupfer und Cadmium geprüft. Die Soxhlet-Extraktion, die saure Veraschung und die Veraschung im Autoklaven wurde zwecks Analyse von Luftproben verglichen, wobei sich das erstgenannte Verfahren als überlegen erwies. Es ist einfach, zuverlässig und bietet geringe Gefahr des Verlustes oder der Einschleppung von Spurenmetallen.

     

In search of ultrastrong Brønsted neutral organic superacids: a DFT study on some cyclopentadiene derivatives

An efficient but reasonably accurate B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) computational procedure showed that pentasubstituted cyclopentadienes such as (CN)5C5H, (NO2)5C5H, and (NC)5C5H containing strongly electron-withdrawing groups are neutral organic superacids of unprecedented strength. The boldface denotes the atom attached to the cyclopentadiene framework. All of them exhibit prototropic tautomerism by forming somewhat more stable structures with C=NH, NO2H, and N=CH exocyclic fragments, respectively. The acidity (DeltaH(acid)) of these is lower, but only to a rather small extent. The DeltaH(acid) enthalpies of these last three tautomers are estimated to be 271, 276, and 282 kcal mol(-1), respectively. Hence, the most stable tautomers of (CN)5C5H and (NC)5C5H represent a legitimate target for synthetic chemists. On the other hand, (NO2)5C5H is less suitable for practical applications, because of its high energy density. The origin of the highly pronounced acidity of these compounds was analyzed by using the recently developed triadic formula. It is found that very high Koopmans' ionization energy (IE)n(Koop) of conjugate bases exerts a decisive influence on acidity. It follows as a corollary that the overwhelming effect leading to very high acidity is due to the properties of the final state. An alternative picture is offered by homodesmotic reactions, wherein the cyclic systems are compared with their linear counterparts. It is found that the acidity of cyclopentadiene (CP) is a consequence of aromatic stabilization in the CP- anion. The extreme acidity of pentacyanocyclopentadiene (CN)5C5H is due to aromatization of the five-membered ring and a strong anionic resonance effect in the resultant conjugate base. The neutral organic superacids predicted by the present calculations may help to bridge the gap between existing very strong acids and bases.     

EPR study of a copper impurity center in a single crystal of 2-thiothymine

EPR spectroscopy was used to study the complex formed in crystals of 5-methyl-2-thiouracil (2-thiothymine) containing traces of copper. The copper impurities, originally present as Cu(I)-complex of 2-thiothymine in the lattice of 2-thiothymine, are transformed into paramagnetic Cu(II)-complex by ionizing radiation. It was found that the complex is planar, the plane being defined by two pairs of S and N atoms, from two adjacent 2-thiothymine molecules. The structure of the complex suggests that a pair of hydrogen bonds between two neighboring molecules is replaced by a stronger Cu-coordination bonding, with two sulfur and two nitrogen atoms as ligands. The spectroscopic parameters (g-tensor, A(63Cu) and A(14N) tensors) are essentially similar to those earlier observed for copper planar centers in other systems.     

Elektrophorese der halogenokomplexe von Hg(II), Bi(III), Cd(II), Pb(II) und -Cu(II) : Chlorokomplexe in chlorwasserstoffsäure

An apparatus for heavy-current and high-tension electrophoresis on filter paper is described This apparatus enables one to avoid the difficulties that occur in electrophoresis in base electrolytes that are highly concentrated or show greater electric conductivity The zones migrate along the paper strips with constant speed and, consequently, it is possible to measure the mobility The effective length of the filter paper strips is 660 mm Correction of the apparent mobility in the porous adsorbent is treated thoroughly.Diagrams of the electrophoretic mobility of the chloro-complexes of Hg(II), Bi(III), Cd(II), Pb(II), and Cu(II) in hydrochloric acid, are given in the experimental part The concentration of the hydrochloric acid varied between 0.1N and 6N In 6N HCl all the metals investigated are present asani onic complexes. Hg, Bi.Cd, and Pb chloro-complexes show a pronounced maximum of mobility in the anionic range. The sequence of the zones in the direction anode to cathode is Hg, B1, Cd, Pb, Lu al 0.1–2.3N HCl and B1, Hg, Cd, Pb.Cu at2.3–6N HCl.Finally, the electrophoretic separation of a mixture of Hg, Bi, Cd, Pb, Cu in 1N, 2N and 4N HCl is illustrated Complete separation of the zones was achieved in each experiment     

The existence of symmetric designs with parameters (105, 40, 15)

The existence of symmetric designs with parameters (105, 40, 15) was shown. © 1999 John Wiley & Sons, Inc. J Combin Designs 7: 17–19, 1999     

Modeling snow crystal growth II: A mesoscopic lattice map with plausible dynamics

We present a local lattice model for the evolution of snow crystals that combines diffusion-limited aggregation with anisotropic attachment kinetics and an idealized quasi-liquid layer. Despite a voluminous modeling literature, this is apparently the first approach that successfully captures the essential form of core and tip instabilities, branch faceting, and other aspects of real snow crystal growth. As parameters are varied, our nearest neighbor system reproduces the basic features of most of the observed varieties of planar snowflakes and offers new insights into their genesis.     

Reflexivity of the commutant and local commutants of an algebraic operator

We show that an algebraic operator on a complex Banach space has reflexive commutant if and only if each zero of the minimal polynomial of the operator is simple. Further, for any operator, the local commutant at an eigenvector is reflexive. On the other hand, for an algebraic operator whose minimal polynomial has at least one zero that is not simple, the local commutant of the operator at a given vector is reflexive precisely when the vector is an eigenvector.