Photoinduced electron transfer in a triad that can be assembled/disassembled by two different external inputs. Toward molecular-level electrical extension cables

We have designed, synthesized, and investigated a self-assembling supramolecular system which mimics, at a molecular level, the function performed by a macroscopic electrical extension cable. The system is made up of three components, 12+, 2-H3+, and 3. Component 12+ consists of two moieties: a [Ru(bpy)3]2+ unit, which plays the role of an electron donor under light excitation, and a DB24C8 crown ether, which fulfills the function of a socket. The wire-type component 2-H3+ is also composed of two moieties, a secondary dialkylammonium-ion center and a bipyridinium unit, which thread into the DB24C8 crown-ether socket of 12+ and the 1/5DN38C10 crown-ether socket 3, respectively. The photochemical, photophysical, and electrochemical properties of the three separated components, of the 12+ superset 2-H3+ and 2-H3+ subset 3 dyads, and of the 12+ superset 2-H3+ subset 3 triad have been investigated in CH2Cl2 solution containing 2% MeCN. Reversible connection/disconnection of the two plug/socket systems can be controlled independently by acid/base and redox stimulation. The behavior of the various different dyads and triad has been monitored by light absorption and emission spectroscopies, as well as by electrochemical techniques. In the fully connected 12+ superset 2-H3+ subset 3 triad, light excitation of the [Ru(bpy)3]2+ unit of component 12+ is followed by electron transfer (k = 2.8 x 108 s-1) to the bipyridinium unit of component 2-H3+, which is plugged into component 3. Possible schemes to obtain improved molecular-level electrical extension cables are discussed.     

Dipole-dipole coupling constant for a directly bonded CH pair--a carbon-13 relaxation study

Multiple-field (4.7, 9.4, 14.1 T) carbon-13 relaxation data are reported for hexamethylenetetramine (HMTA) in the cryosolvent D(2)O/DMSO at 243 K. Under these conditions, the reorientational motion of HMTA is outside of the extreme narrowing range and the relaxation data can be subjected to a quantitative interpretation. Because of the high symmetry of the HMTA molecule, the reorientation must be isotropic. Treating the reorientation as a small-step rotational diffusion of a rigid body, we obtain a rotational correlation time of 1.0 ns and a carbon-proton dipole-dipole coupling constant corresponding to an effective internuclear distance of 114. 2 pm. The harmonic vibrational correction to the dipole-dipole coupling constant, based on a known force field, yields an NMR estimate of the r(alpha) distance of 110.8 +/- 0.3 pm.     

Dynamic rotational characteristics of actinides on empirical approach

In the paper calculation of the moments of inertia for nuclei from the region 87 ≤ Z ≤ 100 and 130 ≤ N ≤ 156 was made in dependence on the angular momentum of their rotational states. The experimental values of the moments of inertia were calculated for rotational energy of the classic rotor in its quantum form, with the use of a simple formula. The moment of inertia term appearing in the formula was treated as a variable. The calculations were carried out on the basis of experimental data for the energies of the rotational levels for 51 bands built on ground states for even-even nuclei and for nuclei with odd mass number A. In addition, 30 rotational bands built on excited states were also analysed in the investigated region in case of even-even nuclei. For many bands and nuclei the considered dependence of the moment of inertia on angular momentum has been found in the analytical form by fitting polynomials to the experimental data. It turned out that obtained results for the moments of inertia made it possible to describe the energies of rotational levels with a relative deviation not greater or only slightly greater than 1%. In general, in the case of 12 bands of ground level the maximum relative deviation of obtained level energies is smaller than 1%.      

Polysialylated-neural cell adhesion molecule (PSA-NCAM) in the human trigeminal ganglion and brainstem at prenatal and adult ages

Background  

The polysialylated neuronal cell adhesion molecule (PSA-NCAM) is considered a marker of developing and migrating neurons and of synaptogenesis in the immature vertebrate nervous system. However, it persists in the mature normal brain in some regions which retain a capability for morphofunctional reorganization throughout life. With the aim of providing information relevant to the potential for dynamic changes of specific neuronal populations in man, this study analyses the immunohistochemical occurrence of PSA-NCAM in the human trigeminal ganglion (TG) and brainstem neuronal populations at prenatal and adult age.     

Solutions of the Dirac–Fock Equations for Atoms¶and Molecules

The Dirac-Fock equations are the relativistic analogue of the well-known Hartree-Fock equations. They are used in computational chemistry, and yield results on the inner-shell electrons of heavy atoms that are in very good agreement with experimental data. By a variational method, we prove the existence of infinitely many solutions of the Dirac-Fock equations "without projector", for Coulomb systems of electrons in atoms, ions or molecules, with Z h 124, N h 41, N h Z. Here, Z is the sum of the nuclear charges in the molecule, N is the number of electrons.     

Nonlinear effects of electrolyte diodes and transistors in a polymer gel medium

The polarization curve of an acid-base interface in a hydrogel medium has a diode characteristic. Two of each such electrolyte diodes can be combined to give an electrolyte transistor. When a salt is added to the alkaline or to the acidic part of a reverse biased electrolyte diode, the current response is highly nonlinear. If the salt is added to the acidic side, even bistability can be observed. This bistability can generate complex oscillations in a base-acid-base electrolyte transistor. These nonlinear effects are studied experimentally and theoretically. While the nonlinear salt effect can be explained with the Nernst-Planck equations, to understand the bistable behavior further investigations are necessary. (c) 1999 American Institute of Physics.     

Effects of chlorine gas exposure on the optical properties of rhodium phthalocyanine films

We investigated the effects of exposing rhodium phthalocyanine films deposited on glass substrates by the Lagmuir-Blodgett technique to chlorine gas. The visual aspect of the films is altered upon chlorination, changing in color from blue to transparent. We performed optical absorption and Raman Scattering measurements on our films prior to and after exposing it to chlorine gas. We observed a pronounced quenching of the characteristic triplet centered around the Q-absorption band at 662 nm as a result of chlorine incorporation. Another absorption band, in the near UV part of the spectrum, is not greatly affected by the process. No new optical structures appear as a consequence of chlorination. Equivalent effects were observed in the Raman spectra. Leaving the previously exposed films in air for several hours results in a slow partial recovery of the optical spectra. This recovery, as well as the amount of original quenching, depends on the amount of time during which the film was exposed to chlorine.     

The Electron Density is Smooth Away from the Nuclei

We prove that the electron densities of electronic eigenfunctions of atoms and molecules are smooth away from the nuclei.     

A Total Synthesis of (±)- Aphidicolin: Regio- and stereoselective conversion of 3α,18-Di-O-benzyl-17-nor-14-aphidicolen-16-one into (±)-aphidicolin

A regio- and steroselective conversion of the totally synthetic 3α, 18-di-O-benzyl-17-nor-14-aphidicolen-16-one (5), into (±)-aphidicolin 1 , by hydroxylation of the 2-methylidenebicyclo[3.2.1] oct-3-ene derivative 6 is described. Compound 5 was a key intermediate in our previously described total synthesis of 2 , which represented a formal synthesis of 1 .