Radical reactions initiated by the photochemical cleavage of carbon-indium bonds of organoindium compounds

Intra- and intermolecular reactions of carbon-centered radicals generated by photolysis of organoindium compounds were examined. The photolysis of vinylindium compounds and indium acetylides provided vinyl and alkynyl radicals, respectively, which were trapped with ethyl iodoacetate giving the corresponding β,γ-unsaturated esters. Allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, underwent an intramolecular radical cyclization to afford the 5-exo-trig product.     

A note on stationarity of types over models in simple theories

We investigate stationarity of types over models in simple theories. In particular, we show that in simple theories with finite SU‐rank, any complete type over a model having Cantor‐Bendixson rank is stationary. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Poly-intercalators Carrying Threading Intercalator Moieties as Novel DNA Targeting Ligands

Threading intercalators are a novel class of intercalators that carry two substituents along the diagonal positions of an aromatic ring. These substituents are projecting out in DNA grooves when bound to DNA. Poly-intercalators carrying threading intercalating parts are quite novel and were recently found to show a unique DNA binding behavior. We review herein two types of poly-intercalators. First, tris-intercalators carrying a threading intercalator part in the middle of the molecule are described. These intercalators appear to intercalate into double stranded DNA in a special binding manner, which we call the penetrating mode, in which all the three intercalating units are arranged linearly with one of them penetrating into the DNA ladder. We synthesized two tris-intercalators ( 3 and 4) of this type and studied their binding behavior for double stranded DNA. All the experimental results were consistent with the proposed penetrating mode. Another type of threading poly-intercalators is a macrocyclic bis-threading intercalator ( 5). We found that this compound can bis-intercalate to double stranded DNA when the base pairing is disrupted temporarily to form a complex with a unique structure like a catenane. On the basis of a study of the interaction of such intercalators we envisage that DNA is a flexible and dynamic entity. These novel families of poly-intercalators will expand the scope of DNA poly-intercalation chemistry with possible medicinal applications.     

Sequential bond energies of Fe+ (CO2)n, n = 1-5, determined by threshold collision-induced dissociation and ab initio theory

Collision-induced dissociation of the Fe+ (CO2)n complexes for n = 1-5 is studied using kinetic energy dependent guided ion beam mass spectrometry. In all cases, the primary products are endothermic loss of an intact neutral ligand from the complex. The cross section thresholds are interpreted to yield 0 K bond energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. These values are compared with density functional theoretical values for all five complexes. Theory provides bond energies in reasonable agreement with experiment for n = 1-4 and predictions for the infrared spectroscopy of these complexes that agree nicely with experimental results of Gregoire and Duncan (J. Chem. Phys. 2002, 117, 2120). Our thermochemical results are also compared with the Fe+ (CO)n and Fe+ (N2)n complexes, previously studied.     

The first hetero-bifunctionalization of the secondary face of beta-cyclodextrin: selective and efficient conversion of the A-ring of a 2A,2B-disulfonate to 2A,3A-epoxymannoside

The A-ring of 2(A),2(B)-O,O-di(mesitylenesulfonyl)-beta-cyclodextrin was converted to 2(A),3(A)-epoxymannoside without affecting the other sulfonylated residue, which affords the first approach to hetero-bifunctionalization at the secondary hydroxyl side of cyclodextrins.     

Terabit all-optical logic based on ultrafast two-dimensional transmission gating

Terabit all-optical complementary logic is proposed using two successive time slots to represent a unique logical status. An organic molecular thin film is used as an array of optically controlled optical switches. By utilizing the planar structure of the film and its ultrafast optical response, proof-of-principle fully optical NOT and AND logic operations were demonstrated with 400-fs interval pulses.     

Configuration-dependent bands in 169Re

High-spin states in ¹⁶⁹Re were studied and resulted in the identification of a strongly coupled band based on the 9/2^-[514] Nilsson state and a decoupled band built on the h _9/2 1/2^-[541] intruder proton orbit. The cranked-shell-model calculations present configuration-dependent deformations that can explain the different band crossing frequencies. The 9/2^-[514] band in ¹⁶⁹Re shows the largest signature splitting at low spin among the known odd-mass Re isotopes. After the alignment of a pair of i _13/2 neutrons, the phase of the splitting is inverted with a significantly reduced amplitude. For the 9/2^-[514] bands in light odd-A Re isotopes, the signature splitting of the Routhians and its relation with the signature dependence of M1 transition matrix elements are investigated in connection with the deviation of nuclear shape from axial symmetry, suggesting an appreciable negative deformation for the very neutron-deficient odd-A Re isotopes. Additionally, a three-quasipariticle band was observed and assigned to be built likely on the configuration.Received: 9 May 2003, Published online: 18 December 2003PACS: 21.10.Re Collective levels - 23.20.-g Electromagnetic transitions - 23.20.Lv transitions and level energies - 27.70. + q      

Kelvin-wave cascade on a vortex in superfluid 4He at a very low temperature

A study by computer simulation is reported of the behavior of a quantized vortex line at a very low temperature when there is continuous excitation of low-frequency Kelvin waves. There is no dissipation except by phonon radiation at a very high frequency. It is shown that nonlinear coupling leads to a net flow of energy to higher wave numbers and to the development of a simple spectrum of Kelvin waves that is insensitive to the strength and frequency of the exciting drive. The results are likely to be relevant to the decay of turbulence in superfluid 4He at very low temperatures.     

Photonic molecule lasing

Lasing at resonantly coupled whispering-gallery mode frequencies is observed in photonic molecules consisting of bispheres of 4.2 and 5.1 microm in diameter placed in a silicon V-groove. We examine spatial profiles of photonic molecule modes by use of frequency-resolved imaging and reveal bonding and antibonding mode features. From the lasing threshold characteristics, we quantitatively measure the quality factor and the spontaneous-emission coupling ratio of the photonic molecule modes and confirm that strong coherent coupling leads to photonic molecule modes.