A pyrrolo-tetrathiafulvalene cage: synthesis and X-ray crystal structure

[reaction: see text] A novel type of tetrathiafulvalene-cage 4 containing three monopyrrolo-tetrathiafulvalene units has been prepared employing a general and efficient synthetic approach. X-ray crystal structure analysis revealed that the cage is able to accommodate solvent molecules within a cavity in the solid state.     

Fluorescent 1,10-phenanthroline-containing oligonucleotides distinguish between perfect and mismatched base pairing

[structure: see text] A fluorescent deoxyuridine analogue is sensitive to the polarity of its environment and exhibits a distinct emission profile in single- vs double-stranded oligonucleotides. Emission-monitored denaturation curves of internally modified dU(phen) duplexes are characteristic of the base opposite dU(phen) and distinguish between perfect and mismatched complementary oligonucleotides.     

Poised on the brink between a bistable complex and a compound

[reaction: see text] An enmeshed supramolecular complex, based on a semi-dumbbell-shaped component containing an asymmetrically substituted tetrathiafulvalene site and a 1,5-dioxynaphthalene site for encirclement by a cyclobis(paraquat-p-phenylene) ring component and with a "speed bump" in the form of an thiomethyl group situated between the two recognition sites, has been self-assembled. This complex is a mixture in acetone solution of two slowly interconverting [2]pseudorotaxanes, one of which is on the verge of being a [2]rotaxane at room temperature.     

In Vitro Degradation of Trimethylene Carbonate Based (Co)polymers

Trimethylene carbonate (TMC) was copolymerized with D ,L ‐lactide (DLLA) or with ε‐caprolactone (CL), and the degradation of melt‐pressed solid copolymer films in phosphate‐buffered saline at pH 7.4 and 37 °C was followed for a period of over two years. The parent homopolymers were used as reference materials. The degradation profile of TMC‐DLLA‐ and TMC‐CL based copolymers was similar and was best described by autocatalyzed bulk hydrolysis, preferentially of ester bonds. The hydrolysis rates varied by two orders of magnitude, depending on polymer composition and physical characteristics under the degradation conditions. TMC‐DLLA copolymers degraded faster than the parent homopolymers. The copolymers lost their tensile strength in less than five months, after which mass loss occurred. Copolymers with 50 or 80 mol‐% of TMC underwent total degradation in eleven months. For TMC‐CL copolymers, a slow and gradual decrease in molecular weight and deterioration of the mechanical performance was observed. These copolymers maintained suitable mechanical properties for seventeen months or longer. Chain scission in the semicrystalline copolymers resulted in an increase in crystallinity. In comparison with the CL homopolymer, the introduction of a small amount of TMC (10 mol‐%) significantly reduced the increase in crystallinity during degradation. Poly(TMC) specimens were dimensionally stable and showed a negligible decrease in molecular weight. A 60% decrease in the initial tensile strength of the polymer samples was observed after two years.

     

Oscillation and Nonoscillation of Higher Order Self-Adjoint Differential Equations

Oscillation and nonoscillation criteria for the higher order self-adjoint differential equation (-1)ⁿ(t^alphay⁽ⁿ⁾)⁽ⁿ⁾+q(t)y = 0 (*) are established. In these criteria, equation (*) is viewed as a perturbation of the conditionally oscillatory equation (-1)ⁿ(t^alphay⁽ⁿ⁾)⁽ⁿ⁾ - µ,t^2n-y = 0, where _n, is the critical constant in conditional oscillation. Some open problems in the theory of conditionally oscillatory, even order, self-adjoint equations are also discussed.     

The theoretical design of neutral planar tetracoordinate carbon molecules with C(C)(4) substructures

Using a new charge-compensation strategy, we designed neutral molecules with perfectly planar C(C)(4)-type tetracoordinate carbon arrangements (ptC) employing DFT computations. These designs, based on the planar preference of methane dications, replace two remote carbons in spiroalkaplanes by borons or two remote hydrogens by BH(3) groups; the two formally anionic boron units which result compensate the formal double positive charge on the central ptC's. The LUMOs correspond to the "wasted" lone pair HOMOs of the alkaplanes. As compared to the latter, pi occupancies on the central carbon are much smaller (less than 0.7e), and the IPs are much larger. The newly predicted compounds utilize all of the electrons more effectively. There are no lone pairs, and the ptC-C bond lengths are ca. 1.50 A. The Wiberg bond index sums of the ptC's are near 3.2, and the boron sums are close to 4.     

Electron release of fare-gas atomic clusters under an intense laser pulse

Calculating the energy absorption of atomic clusters as a function of the laser pulse length T we find a maximum for a critical T(*). We show that T(*) can be linked to an optimal cluster radius R(*). The existence of this radius can be attributed to the enhanced ionization mechanism originally discovered for diatomic molecules. Our findings indicate that enhanced ionization should be operative for a wide class of rare-gas clusters. From a simple Coulomb-explosion ansatz, we derive an analytical expression relating the maximum energy release to a suitably scaled expansion time which can be expressed with the pulse length T(*).     

Nature of low-energy dipole strength in nuclei: the case of a resonance at particle threshold in 208Pb

A high-resolution (gamma,gamma') study of the electric dipole response in 208Pb at the S-DALINAC reveals a resonance structure centered around the neutron emission threshold. Microscopic quasiparticle phonon model calculations in realistic model spaces including the coupling to complex configurations are able to describe the data in great detail. The resonance is shown to result from surface density oscillations of the neutron skin relative to an approximately isospin-saturated core. It also forms an integral part of a toroidal E1 mode representing an example of vortex collective motion in nuclei.     

Imaging delocalized electron clouds: photoionization of C(60) in Fourier reciprocal space

The dynamics of the photoionization of the two outermost orbitals of C(60) has been studied in the oscillatory regime from threshold to the carbon K edge. We show that geometrical properties of the fullerene electronic hull, such as its diameter and thickness, are contained in the partial photoionization cross sections by examining ratios of partial cross sections as a function of the photon wave number in the Fourier conjugated space. Evaluated in this unconventional manner photoemission data reveal directly the desired spatial information.     

Structure determination of gas-phase niobium and tantalum carbide nanocrystals via infrared spectroscopy

Niobium and tantalum carbide clusters have been isolated in the gas phase and irradiated with intense tunable infrared (IR) light. Stable neutral clusters are selectively ionized and subsequently detected in a mass spectrometer. By tuning the IR frequency, infrared multiphoton absorption spectra are obtained for a whole range of clusters. These mass-selective IR spectra lead to insights into the structures of small niobium and tantalum carbide clusters and nanocrystals.