He I photoelectron spectra and gas-phase electronic structures of end-functionalized [3]- and [5]-ladderanes

[3]- and [5]-ladderanes obtained by way of template-controlled syntheses conducted in the organic solid state have been characterized via He I photoelectron (PE) spectroscopy. The results provide a first correlation with X-ray crystallographic structure data and establish the reliability of quantum chemical DFT (B3LYP/6-31G*) and ab initio HF calculations in predicting geometrical and electronic structures of molecular ladder frameworks.     

The cosmology of the nonsymmetric theory of gravitation

We show that during cosmological inflation the nonsymmetric metric tensor theory of gravitation develops a spectrum which is potentially observable by cosmic microwave background observations, and may be the most sensitive probe of the scale of cosmic inflation.     

Dynamics of superhorizon photons during inflation with vacuum polarization

We study asymptotic dynamics of photons propagating in the polarized vacuum of a locally de Sitter Universe. The origin of the vacuum polarization is fluctuations of a massless, minimally coupled, scalar, which we model by the one-loop vacuum polarization tensor of scalar electrodynamics. We show that late time dynamics of the electric field on superhorizon scales approaches that of an Airy oscillator. The magnetic field amplitude, on the other hand, asymptotically approaches a nonvanishing constant (plus an exponentially small oscillatory component), which is suppressed with respect to the initial (vacuum) amplitude. This implies that the asymptotic photon dynamics is more intricate than that of a massive photon obeying the local Proca equation.     

Automated registration of sequential breath-hold dynamic contrast-enhanced MR images: a comparison of three techniques

Dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) is increasingly in use as an investigational biomarker of response in cancer clinical studies. Proper registration of images acquired at different time points is essential for deriving diagnostic information from quantitative pharmacokinetic analysis of these data. Motion artifacts in the presence of time-varying intensity due to contrast enhancement make this registration problem challenging. DCE-MRI of chest and abdominal lesions is typically performed during sequential breath-holds, which introduces misregistration due to inconsistent diaphragm positions and also places constraints on temporal resolution vis-à-vis free-breathing. In this work, we have employed a computer-generated DCE-MRI phantom to compare the performance of two published methods, Progressive Principal Component Registration and Pharmacokinetic Model-Driven Registration, with Sequential Elastic Registration (SER) to register adjacent time-sample images using a published general-purpose elastic registration algorithm. In all three methods, a 3D rigid-body registration scheme with a mutual information similarity measure was used as a preprocessing step. The DCE-MRI phantom images were mathematically deformed to simulate misregistration, which was corrected using the three schemes. All three schemes were comparably successful in registering large regions of interest (ROIs) such as muscle, liver, and spleen. SER was superior in retaining tumor volume and shape, and in registering smaller but important ROIs such as tumor core and tumor rim. The performance of SER on clinical DCE-MRI data sets is also presented.     

Fullerene Graphs with Exponentially Many Perfect Matchings

We show that for all sufficiently large even p there is a fullerene graph on p vertices that has exponentially many perfect matchings in terms of the number of vertices. Further, we show that all fullerenes with full icosahedral symmetry group have exponentially many perfect matchings and indicate how such results could be extended to the fullerenes with lower symmetry.     

Relatively Moving Systems in “True Transformations Relativity”

In this paper the physical systems consisting of relatively moving subsystems are considered in the true transformations relativity. It is found in a manifestly covariant way that there is a second-order electric field outside stationary current-carrying conductor. It is also found that there are opposite charges on opposite sides of a square loop with current and these charges are invariant charges.     

Separation of structurally related peptides by open-tubular capillary electrochromatography using (metallo)porphyrins as the adsorbed stationary phase

Several (metallo)porphyrins, particularly the porphyrin derivative tetraphenylporphyrin, and complexes of porphyrin derivatives with metal ions (Zn2+, Cu2+, Ni2+, Co2+, Co3+) have been employed as the stationary phase physically adsorbed onto the inner fused-silica capillary surface for open-tubular capillary electrochromatography, and applied for the separation of structurally related peptides. Four octapeptides, derivatives of the B23-B30 fragment of the B-chain of human insulin with minor changes in their sequences (presence of lysine or ornithine in position B-29, presence or absence of phenylacetyl protecting group on the amino group of lysine/ornithine or N-terminal amino group of glycine), were studied as model analytes. Separations were performed both in alkaline (pH 9.0) and in acidic (pH 2.25) background electrolytes, and the changes in the migration/retention behaviour of the model set of peptides were investigated with respect to the porphyrin periphery/central metal atom and the charge of the octapeptides modified. The key moment of successful separation of these peptides seems to be the accessibility of functional groups of the peptides to the interaction with the modifiers tested herein.     

Heats of atomization of conjugated hydrocarbons by a new semiempirical method

Heats of atomization of a range of conjugated hydrocarbons are calculated by a semiempirical method which combines characteristic features of the MO and the VB theory. The -ground state of each hydrocarbon is represented as a linear combination of Kekulé structures where, unlike the VB theory, each Kekulé structure is a determinant containing bond Orbitals. In this approach only the Hückel parameter has to be adjusted. Experimental heats of atomization are by this method reproduced approximately equally well as by the more sophisticated SCF-MO approach. The use of this method is however much simpler since it amounts to a single diagonalization of a matrix of the order equal to the number of Kekulé structures only.     

Vibrational isotope effect of linear and planar molecules: Deuterated bromoethenes

Linear (planar) molecules A and B which are identical except for isotopic substitutions at the atomic sites are considered. Stretching (bending, out-of-plane) frequencies _k and normal modes _k of the isotopically perturbed molecule B are expressed in terms of stretching (bending, out-of-plane) frequencies _i and the corresponding normal modes _i of the unperturbed molecule A. Complete specification of the unperturbed normal modes is not required. All that is needed are stretching (bending, out-of-plane) amplitudes | _i of the normal modes _i at those sites that are affected by isotopic substitution. The rule which interlaces frequencies _k of molecule A with frequencies _i of molecule B is derived. Given two isotopic molecules A and B that differ by a single isotopic substitution at site , the inversion relation is derived. This relation expresses unperturbed stretching (bending, out-of-plane) amplitudes at the site in terms of stretching (bending, out-of-plane) frequencies of molecules A and B . As an example, out-of-plane vibrations of deuterated bromoethene were considered. In the simplest method 12 out-of-plane frequencies of four polydeuterated bromoethenes were calculated from 12 out-of-plane frequencies of bromoethene and three monodeuterated bromoethenes. Standard deviation of thus calculated frequencies from experimental frequencies is =2.74 cm^–1. In another method, 15 out-of-plane frequencies of four polydeuterated bromoethenes and selected monodeuterated bromoethene are calculated from 9 out-of-plane frequencies of bromoethene and the remaining two monodeuterated bromoethenes. Depending on which monodeuterated bromoethene is selected (1-, cis- or trans-), standard deviation of thus obtained frequencies from experimental frequencies is 1=2.84 cm^–1, c=2.96 cm^–1 and t=2.72 cm^–1.