Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

Death Aesthetization in Contemporary Artistic Practices

Starting from the famous and enigmatic quotation of the Aristotle’s Poetics, who argues that the human has a natural desire and pleasure to see corpses if mediated by art, is intended to show the relationship between the attraction for the horror and some contemporary art practices surrounding the depiction of death, particularly with regard to the ultimate use of the human corpse as an artistic resource. Avoiding any kind of ethical approach or questioning of the limits of the artistic production, is meant to highlight the phenomenon through the examples brought out by the work of some contemporary artists such as Andy Warhol, Eric Fischl, Damien Hirst, Von Hagens, Andres Serrano, Joel-Peter Witkin and Teresa Margolles: From those who use the corpse in and turn it in something aesthetically pleasant, to others who turn human corpses in sculptures of scientific value, and further other kind of artists who assume the morbid and dramatic life of the corpse in their art production as something structural.

Synthesis of (+)-piclavines A1 and A2

Piclavines AI and A2 have been synthesised for the first time. The route is short with the key step being the reaction of a bicyclic N-acyl iminium ion with 3-trimethysilyl-1-decene. This convergent strategy gave exclusively compounds in which the pendant decenyl group was axial, as a 6:1 mixture of E:Z-alkene diastereoisomers. Reduction of the lactam carbonyl group gave a 6:1 mixture of piclavines Al and A2, (C) 2000 Published by Elsevier Science Ltd.

Expedient synthesis of (+)-trans-5-allylhexahydroindolizidin-3-one

Treatment of the bicyclic iminium ion derived from 5-methoxyhexahydroindolizidin-3-one with allyltrimethylsilane gave exclusively the diastereoisomer in which the allyl group was axial. This substrate is a useful precursor to 5-propyl-3-alkylindolizidine alkaloids. (C) 1999 Elsevier Science Ltd. All rights reserved.

Socio-economic inequalities in cerebral palsy prevalence in the United Kingdom: a register-based study

Evidence is unclear as to whether there is a socio-economic gradient in cerebral palsy (CP) prevalence beyond what would be expected from the socio-economic gradient for low birthweight, a strong risk factor for CP. We conducted a population-based study in five regions of the UK with CP registers, to investigate the relationship between CP prevalence and socio-economic deprivation, and how it varies by region, by birthweight and by severity and type of CP. The total study population was 1 657 569 livebirths, born between 1984 and 1997. Wards of residence were classified into five quintiles according to a census-based deprivation index, from Q1 (least deprived) to Q5 (most deprived). Socio-economic gradients were modelled by Poisson regression, and region-specific estimates combined by meta-analysis.

The prevalence of postneonatally acquired CP was 0.14 per 1000 livebirths overall. The mean deprivation gradient, expressed as the relative risk in the most deprived vs. the least deprived quintile, was 1.86 (95% confidence interval [95% CI 1.19, 2.88]). The prevalence of non-acquired CP was 2.22 per 1000 livebirths. For non-acquired CP the gradient was 1.16 [95% CI 1.00, 1.35]. Evidence for a socio-economic gradient was strongest for spastic bilateral cases (1.32 [95% CI 1.09, 1.59]) and cases with severe intellectual impairment (1.59 [95% CI 1.06, 2.39]). There was evidence for differences in gradient between regions. The gradient of risk of CP among normal birthweight births was not statistically significant overall (1.21 [95% CI 0.95, 1.54]), but was significant in two regions. There was non-significant evidence of a reduction in gradients over time.

The reduction of the higher rates of postneonatally acquired CP in the more socioeconomically deprived areas is a clear goal for prevention. While we found evidence for a socio-economic gradient for non-acquired CP of antenatal or perinatal origin, the picture was not consistent across regions, and there was some evidence of a decline in inequalities over time. The steeper gradients in some regions for normal birthweight cases and cases with severe intellectual impairment require further investigation.

Strengthening Clinical Cancer Research in the United Kingdom

BACKGROUND: In 1999, 270,000 cases of cancer were registered in the United Kingdom, placing a large burden on the NHS. Cancer outcome data in 1999 suggested that UK survival rates were poorer than most other European countries. In the same year, a Department of Health review noted that clinical trials accrual was poor (

Resource access needs and capabilities as mediators of the relationship between VC firm size and syndication

Drawing from the resource-based view and transaction costs economics, we develop a theoretical framework to explain why small and large firms face different levels of resource access needs and resource access capabilities, which mediate the relationship between firm size and hybrid governance. Employing a sample of 317 venture capital firms, drawn across six European countries, we empirically assess our framework in the context of venture capital syndication. We estimate a path model using structural equation modeling and find, consistent with our theoretical framework, mediating effects of different types of resource access needs and resource access capabilities between VC firm size and syndication frequency. These findings advance the small business literature by highlighting the trade-offs that size imposes on firms that seek to manage their access to external resources through hybrid governance strategies.

Form Follows Media::What is The Matrix as Film, Animation, Game and Comics?

In the digital age, the hyperspace of virtual reality systems stands out as a new spatial notion creating a parallel world to the space we live in. In this alternative realm, the body transforms into a hyperbody, and begins to follow the white rabbit. Not only in real world but also in the Matrix world. The Matrix project of Andy and Larry Wachowski started with a feature film released in 1999. However, The Matrix is not only a film (trilogy). It is a concept, a universe that brings real space and hyperspace together. It is a world represented not only in science fiction films but also in The Animatrix that includes nine animated Matrix films directed by Peter Chung, Andy Jones, Yoshiaki Kawajiri and others, four of which are written by the Wachowskis. The same universe is used in Enter the Matrix, a digital game whose script was written and directed by the brothers and a comic book, The Matrix Comics, which includes twelve different stories by artists like Neil Gaiman and Goef Darrow. The Wachowskis played an active role in the creation and realization of all these “products” of different media. The comic book came last (November 2003), however it is possible to argue that everything came out of comics – the storyboards of the original film. After all the Wachowskis have a background in comics.

In this study, I will focus on the formal analysis of the science fiction world of The Matrix - as a representation of hyperspace - in different media, feature film, animated film, digital game and comic book, focusing on diverse forms of space that come into being as a result of medium differences. To unfold the different formal characters of film, animation, game and comics, concepts and features including framing, flattening, continuity, movement, montage, sound/text, light and color will be discussed. An analysis of these products will help to open up a discussion on the relation of form, media and representation.

Increasing entanglement through engineered disorder in the random Ising chain

The ground-state entanglement entropy between block of sites in the random Ising chain is studied by means of the Von Neumann entropy. We show that in presence of strong correlations between the disordered couplings and local magnetic fields the entanglement increases and becomes larger than in the ordered case. The different behavior with respect to the uncorrelated disordered model is due to the drastic change of the ground state properties. The same result holds also for the random three-state quantum Potts model.