Free radical-mediated lipid peroxidation and systemic nitric oxide bioavailability:implications for postexercise hemodynamics

The metabolic vasodilator mediating postexercise hypotension (PEH) is poorly understood. Recent evidence suggests an exercise-induced reliance on pro-oxidant-stimulated vasodilation in normotensive young human subjects, but the role in the prehypertensive state is not known.

Photodetachment as destruction mechanism for CN- and C3N- anions in circumstellar envelopes

Absolute photodetachment cross sections of two anions of astrophysical importance CN- and C3N- were measured to be (1.18 +- (0.03)_stat (0.17)_sys) * 10^-17 cm^2 and (1.43 +- (0.14)_stat (0.37)_sys) * 10^-17 cm^2 respectively at the ultraviolet wavelength of 266 nm (4.66 eV). These relatively large values of the cross sections imply that photodetachment can play a major role in the destruction mechanisms of these anions particularly in photon-dominated regions. We have therefore carried out model calculations using the newly measured cross sections to investigate the abundance of these molecular anions in the cirumstellar envelope of the carbon-rich star IRC+10216. The model predicts the relative importance of the various mechanisms of formation and destruction of these species in different regions of the envelope. UV photodetachment was found to be the major destruction mechanism for both CN- and C3N- anions in those regions of the envelope, where they occur in peak abundance. It was also found that photodetachment plays a crucial role in the degradation of these anions throughout the circumstellar envelope.

Investigating the Potential Impact of Four-dimensional Computed Tomography (4DCT) on Toxicity, Outcomes and Dose Escalation for Radical Lung Cancer Radiotherapy

AIMS: To investigate the potential dosimetric and clinical benefits predicted by using four-dimensional computed tomography (4DCT) compared with 3DCT in the planning of radical radiotherapy for non-small cell lung cancer.

MATERIALS AND METHODS:
Twenty patients were planned using free breathing 4DCT then retrospectively delineated on three-dimensional helical scan sets (3DCT). Beam arrangement and total dose (55 Gy in 20 fractions) were matched for 3D and 4D plans. Plans were compared for differences in planning target volume (PTV) geometrics and normal tissue complication probability (NTCP) for organs at risk using dose volume histograms. Tumour control probability and NTCP were modelled using the Lyman-Kutcher-Burman (LKB) model. This was compared with a predictive clinical algorithm (Maastro), which is based on patient characteristics, including: age, performance status, smoking history, lung function, tumour staging and concomitant chemotherapy, to predict survival and toxicity outcomes. Potential therapeutic gains were investigated by applying isotoxic dose escalation to both plans using constraints for mean lung dose (18 Gy), oesophageal maximum (70 Gy) and spinal cord maximum (48 Gy).

RESULTS:
4DCT based plans had lower PTV volumes, a lower dose to organs at risk and lower predicted NTCP rates on LKB modelling (P < 0.006). The clinical algorithm showed no difference for predicted 2-year survival and dyspnoea rates between the groups, but did predict for lower oesophageal toxicity with 4DCT plans (P = 0.001). There was no correlation between LKB modelling and the clinical algorithm for lung toxicity or survival. Dose escalation was possible in 15/20 cases, with a mean increase in dose by a factor of 1.19 (10.45 Gy) using 4DCT compared with 3DCT plans.

CONCLUSIONS:
4DCT can theoretically improve therapeutic ratio and dose escalation based on dosimetric parameters and mathematical modelling. However, when individual characteristics are incorporated, this gain may be less evident in terms of survival and dyspnoea rates. 4DCT allows potential for isotoxic dose escalation, which may lead to improved local control and better overall survival.

Motion Management for Radical Radiotherapy in Non-small Cell Lung Cancer

Intrafraction tumour motion is an issue that is of increased interest in the era of image-guided radiotherapy. It is particularly relevant for non-small cell lung cancer, for which a number of recent developments are in use to aid with motion management in the delivery of radical radiotherapy. The ability to deliver hypofractionated ablative doses, such as in stereotactic radiotherapy, has been aided by improvements in the ability to analyse tumour motion and amend treatment delivery. In addition, accounting for tumour motion can enable dose escalation to occur by reducing the normal tissue being irradiated by virtue of a reduction in target volumes. Motion management for lung tumours incorporates five key components: imaging, breath-hold techniques, abdominal compression, respiratory tracking and respiratory gating. These will be described, together with the relevant benefits and associated complexities. Many studies have described improved dosimetric coverage and reduced normal tissue complication probability rates when using motion management techniques. Despite the widespread uptake of many of these techniques, there is a paucity of literature reporting improved outcome in overall survival and local control for patients whenever motion management techniques are used. This overview will review the extent of lung tumour motion, ways in which motion is detected and summarise the key methods used in motion management.

Glycolaldehyde Formation via the Dimerisation of the Formyl Radical

Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints.

Polymerisable squaramide receptors for anion binding and sensing

A novel series of polymerisable squaramides has been synthesised in high yields using simple chemical reactions, and evaluated in the binding of anionic species. These vinyl monomers can be used as functional building blocks in co-polymerisations with a plethora of co-monomers or cross-linkers, grace to their compatibility with free-radical polymerisation reactions. Aromatic substituted squaramides were found to be the strongest receptors, while binding of certain anions was accompanied by a strong colour change, attributed to the de-protonation of the squaramide. The best performing squaramide monomers were incorporated in molecularly imprinted polymers (MIPs) targeting a model anion and their capacities and selectivity were evaluated by rebinding experiments. Polymers prepared using the new squaramide monomers were compared to urea based co-polymers, and were found to contain up to 80% of the theoretical maximum number of binding sites, an exceptionally high value compared to previous reports. Strong polymer colour changes were observed upon rebinding of certain anions, equivalent to those witnessed in solution, paving the way for application of such materials in anion sensing devices.



Graphical abstract: Polymerisable squaramide receptors for anion binding and sensing

Asymmetric Total Synthesis of (+)-Inthomycin C Via O-Directed Free Radical Alkyne Hydrostannation with Ph3SnH and Catalytic Et3B: Reinstatement of the Zeeck-Taylor (3R)-Structure for (+)-Inthomycin C

A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (−)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (−)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama’s (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor’s original (3R)-stereostructure for (+)-inthomycin C is correct.

Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling

Abstract Image

Herein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.

A New Mechanism for Hydroxyl Radical Production in Irradiated Nanoparticle Solutions

The absolute yield of hydroxyl radicals per unit of deposited X-ray energy is determined for the first time for irradiated aqueous solutions containing metal nanoparticles based on a “reference” protocol. Measurements are made as a function of dose rate and nanoparticle concentration. Possible mechanisms for hydroxyl radical production are considered in turn: energy deposition in the nanoparticles followed by its transport into the surrounding environment is unable to account for observed yield whereas energy deposition in the water followed by a catalytic-like reaction at the water-nanoparticle interface can account for the total yield and its dependence on dose rate and nanoparticle concentration. This finding is important because current models used to account for nanoparticle enhancement to radiobiological damage only consider the primary interaction with the nanoparticle, not with the surrounding media. Nothing about the new mechanism appears to be specific to gold, the main requirements being the formation of a structured water layer in the vicinity of the nanoparticle possibly through the interaction of its charge and the water dipoles. The massive hydroxyl radical production is relevant to a number of application fields, particularly nanomedicine since the hydroxyl radical is responsible for the majority of radiation-induced DNA damage.

Formation and characterization of carbon-radical precursors in char steam gasification

Highly reactive radicals play an important role in high-temperature gasification processes. However, the effect of radicals on gasification has not been systematically investigated. In the present study, the formation of carbon-radical precursors using atomic radicals such as OH, O, and H and molecules such as H₂ and O₂ was characterized, and the effect of the precursors on the adsorption step of steam char gasification was studied using quantum chemistry methods. The results revealed that the radicals can be chemisorbed exothermically on char active sites, and the following order of reactivity was observed: O > H₂ > H > OH > O ₂. Moreover, hydrogen bonds are formed between steam molecules and carbon-radical complexes. Steam molecule adsorption onto carbon-O and carbon-OH complexes is easier than adsorption onto clean carbon surfaces. Alternatively, adsorption on carbon-O₂, carbon-H₂, and carbon-H complexes is at the same level with that of clean carbon surfaces; thus, OH and O radicals accelerate the physical adsorption of steam onto the char surface, H radical and O₂ and H₂ molecules do not have a significant effect on adsorption. © 2010 American Chemical Society.

The Politics of Observation:Radical Psychiatry and Social Documentary

How did the counter-cultural aims of Radical Psychiatry coincide with those of documentary filmmaking in the 1960s? Where the forms and structures of new approaches to the documentary necessarily complicit in promoting the clinical and anti-clinical practices, and wider political agenda, of Radical Psychiatry? How did the documentary deal with the ethical, aesthetic, and audience-related issues associated with filming personalities and environments associated with Radical Psychiatry? How did Radical Psychiatry and the documentary shape postwar discourses on trauma, especially within conflict and post-conflict (PTSD) contexts? What is the legacy of Radical Pschiatry today, and how has it been explored by contemporary documentray film?

This article addresses these question by examining a range of documentaries dealing with the radical and 'anti-psychiatric' ideas and methods of figures such as R.D.Laing, David Cooper, Jan Bastiaans, Timothy Leary, and Franco Basaglia. Films analysed include Peter Robinson's Asylum (1972) and Psychiatry and Violence (1973); Ah, Sunflower (Klinkert and Sinclair, 1967); Anatomy of Violence (Davis, 1967); Turn On, Tune In, Drop Out (Robin Clarke, 1967), W. R. - Mysteries of the Organism (Makavejev, 1971); Raymond Depardon's San Clemente (1980) and Urgences (1988); and Louis van Gasteren's trilogy Now Do You Get it Why I am Crying (1969), The Price of Survival (2003), and There is No Plane to Zagreb (2012). 
The article concludes with a discussion of Nicolas Philibert's Every Little Thing (1997) within the context of the French documentary tradition and the film's more immediate subject - the famous clinic at La Borde established by Jean Oury, and associated with the methods and theories of figures such as Jacques
 Lacan, Francesc Tosquelles, Franz Fanon, and Félix Guattari.

A fluorescence model of the C3 radical in comets

Theoretical resonance fluorescence calculations are presented of the triatomic C3 radical and are compared with observations of the C3 emission in comets Hale-Bopp and de Vico. A theoretical model of the C3 vibration-rotational structure in the A1Piu - X1Sigmag + electronic system is introduced. The model takes into account the detailed structure of the bending mode nu2 which is responsible for the emission of the 4050 Å group. A total of 1959 levels are considered, with 515 levels in the ground state. The main effort is to model high-resolution spectra of the 4050 Å emission in comets C/1995 O1 Hale-Bopp and 122P/1995 S1 de Vico. The agreement between observed and theoretical spectra is good for a value of the dipole moment derivative of dmu/dr ~ 2.5 Debye Å-1. The modeled C3 emission exhibits a pronounced Swings effect. Based on observations made with William Herschel Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias, and on observations made at the McDonald Observatory, which is operated by the University of Texas at Austin, USA.