Total Ion Spectra versus Segmented Total Ion Spectra as Preprocessing Tools for Gas Chromatography - Mass Spectrometry Data.

Alignment of fire debris data from GC-MS for chemometric analysis is challenged by highly variable, uncontrolled sample and matrix composition. The total ion spectrum (TIS) obviates the need for alignment but loses all separation information. We introduce the segmented total ion spectrum (STIS), which retains the advantages of TIS while retaining some retention information.

Hepatic heterotopia in congenital diaphragmatic anomaly.

An antenatally diagnosed case of a left congenital diaphragmatic hernia is reported. The diaphragmatic eventration hernia sac consisted of a sheet of ectopic liver tissue in continuity with a hypoplastic left lobe which formed the medial anterior and posterior walls of the hernia is presented. The operative management of this combination of defects has not previously been described in English literature.

Understanding the interaction of the porphyrin macrocycle to reactive metal substrates: structure, bonding, and adatom capture.

We investigate the adsorption and conformation of free-base porphines on Cu(110) using STM, reflection absorption infrared spectroscopy, and periodic DFT calculations in order to understand how the central polypyrrole macrocycle, common to all porphyrins, interacts with a reactive metal surface. We find that the macrocycle forms a chemisorption bond with the surface, arising from electron donation into down-shifted and nearly degenerate unoccupied porphine π-orbitals accompanied with electron back-donation from molecular π-orbitals. Our calculations show that van der Waals interactions give rise to an overall increase in the adsorption energy but only minor changes in the adsorption geometry and electronic structure.

Unexpected deformations induced by surface interaction and chiral self-assembly of Co(II)-tetraphenylporphyrin (Co-TPP) adsorbed on Cu(110): a combined STM and periodic DFT study.

In a combined scanning tunnelling microscopy (STM) and periodic density functional theory (DFT) study, we present the first comprehensive picture of the energy costs and gains that drive the adsorption and chiral self-assembly of highly distorted Co(II)-tetraphenylporphyrin (Co-TPP) conformers on the Cu(110) surface. Periodic, semi-local DFT calculations reveal a strong energetic preference for Co-TPP molecules to adsorb at the short-bridge site when organised within a domain. At this adsorption site, a substantial chemical interaction between the molecular core and the surface causes the porphyrin macrocycle to accommodate close to the surface and in a flat geometry, which induces considerable tilting distortions in the phenyl groups.

A comparative study examining open inguinal herniotomy with and without hernioscopy to laparoscopic inguinal hernia repair in a pediatric population.

Aims: Open herniotomy with or without hernioscopy has been performed in our unit for a decade. Since 2005 the laparoscopic repair was also introduced. The aims of this study were: (1) to compare detection rates for direct visualization of the contralateral deep inguinal ring via the known sac using a 70 degrees scope and via umbilical 30 degrees laparoscopy and (2) to compare operative timings, metachronous and recurrence rates for the three different management pathways for inguinal hernia.

Ciliopathy spectrum expanded? Jeune syndrome associated with foregut dysmotility and malrotation.

We report the association and surgical management of gastrointestinal dysmotility and malrotation with Jeune asphyxiating thoracic dystrophy (JATD), an autosomal recessive condition that often results in respiratory failure due to a small rib cage. A 4-month-old male with JATD presented with vomiting and aspiration pneumonitis compounding already severe respiratory morbidity. A contrast study revealed esophageal and gastric dysmotility with associated malrotation.

Racemic versus enantiopure alanine on Cu(110): an experimental study.

The adsorption of racemic alanine on the Cu(110) surface has been compared to that of enantiopure alanine using low-energy electron diffraction (LEED), reflection absorption infrared spectroscopy (RAIRS), and scanning tunneling microscopy (STM). No evidence of chiral resolution at the surface was observed for the racemic system, indicating that the formation of separate enantiopure areas is not preferred. Also, in contrast to the enantiopure system, no chirally organized phase was observed for the racemic system.

Down in the mumps.

A 10-week-old female infant presented with a right-sided facial swelling without any constitutional symptoms. The swelling was nontender, nonfluctuant, with no erythema or induration. On the basis of the clinical picture, magnetic resonance imaging findings and serology, a diagnosis of unilateral mumps parotitis was made.