Model of a polymer chain twisted inside a statistical segment. Poly(3‐hexylthiophene) in chloroform solutions

A set of hydrodynamic methods in extremely dilute solutions (determination of intrinsic viscosity [η ], translational diffusion D and flotation in a centrifugal field s ) was used in the studies of conformational properties, dimensions and equilibrium rigidity of individual molecules of a series of samples of poly(3‐hexylthiophene). Absolute molecular masses M _sD were determined. The Mark–Kuhn–Houwink equations for the range of M _sD from 2240 to 15 300 g mol^?1 are given. For the first time, an analysis of conformational properties and equilibrium flexibility of poly(3‐hexylthiophene) molecules was carried out using the model of a statistical segment containing a twisted polymer chain. © 2017 Society of Chemical Industry     

The nanometre-scale physiology of bone: steric modelling and scanning transmission electron microscopy of collagen�Cmineral structure

The nanometre-scale structure of collagen and bioapatite within bone establishes bone''s physical properties, including strength and toughness. However, the nanostructural organization within bone is not well known and is debated. Widely accepted models hypothesize that apatite mineral (‘bioapatite’) is present predominantly inside collagen fibrils: in ‘gap channels’ between abutting collagen molecules, and in ‘intermolecular spaces’ between adjacent collagen molecules. However, recent studies report evidence of substantial extrafibrillar bioapatite, challenging this hypothesis. We studied the nanostructure of bioapatite and collagen in mouse bones by scanning transmission electron microscopy (STEM) using electron energy loss spectroscopy and high-angle annular dark-field imaging. Additionally, we developed a steric model to estimate the packing density of bioapatite within gap channels. Our steric model and STEM results constrain the fraction of total bioapatite in bone that is distributed within fibrils at less than or equal to 0.42 inside gap channels and less than or equal to 0.28 inside intermolecular overlap regions. Therefore, a significant fraction of bone''s bioapatite (greater than or equal to 0.3) must be external to the fibrils. Furthermore, we observe extrafibrillar bioapatite between non-mineralized collagen fibrils, suggesting that initial bioapatite nucleation and growth are not confined to the gap channels as hypothesized in some models. These results have important implications for the mechanics of partially mineralized and developing tissues.     

Human performance under two different command and control paradigms

The paradoxical behaviour of a new command and control concept called Network Enabled Capability (NEC) provides the motivation for this paper. In it, a traditional hierarchical command and control organisation was pitted against a network centric alternative on a common task, played thirty times, by two teams. Multiple regression was used to undertake a simple form of time series analysis. It revealed that whilst the NEC condition ended up being slightly slower than its hierarchical counterpart, it was able to balance and optimise all three of the performance variables measured (task time, enemies neutralised and attrition). From this it is argued that a useful conceptual response is not to consider NEC as an end product comprised of networked computers and standard operating procedures, nor to regard the human system interaction as inherently stable, but rather to view it as a set of initial conditions from which the most adaptable component of all can be harnessed: the human.     

CdS-sensitized TiO2 in phenazopyridine photo-degradation: Catalyst efficiency,stability and feasibility assessment

Mineralization of phenazopyridine, 1, in water, under solar-simulator radiation was efficiently achieved using nanoparticle CdS-sensitized rutile TiO₂, TiO₂/CdS, 2, as photo-catalysts. Despite that, 2 showed two main drawbacks. Firstly, the system was difficult to recover by simple filtration, and demanded centrifugation. Secondly, the sensitizer CdS showed relatively high tendency to leach out hazardous Cd²⁺ ions under photo-degradation reaction conditions. In an attempt to solve out such difficulties, 2 was supported onto sand surface. The sand/TiO₂/CdS system, 3, was easier to recover but showed slightly lower catalytic activity compared to 2. On the other hand, the support failed to prevent leaching of Cd²⁺. This indicates limited future applicability of CdS-sensitized TiO₂ photo-catalyst systems, in solar-based water purification strategies, unless leaching out tendency is completely prevented.     

A systematic methodology for kinetic modeling of chemical reactions applied to n‐hexane hydroisomerization

Kinetic modeling provides chemical engineers with a unique opportunity to better understand reaction kinetics in general and the underlying chemistry in particular. How to systematically approach a modeling assignment in chemical reaction kinetics is typically less clear, especially for novices in the field. The proposed modeling methodology pursues an adequate compromise between statistical significance and physical meaning of the kinetic model and the corresponding parameters and typically results in models of an appropriate complexity. It comprises the following activities: (1) data analysis, aiming at qualitative information on the reaction mechanism and corresponding rate equations, (2) model regression to quantify this information via optimal parameter values, and (3) validation of the statistical significance and physical meaning of the parameter estimates. This methodology is successfully applied to n‐hexane hydroisomerization on a bifunctional catalyst. © 2014 American Institute of Chemical Engineers AIChE J, 61: 880–892, 2015     

Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

A tool for the generation of decomposition schemes of large molecules has been developed. These decomposition schemes contain radicals which can be eliminated from the model equations if both the μ‐hypothesis and the pseudosteady‐state approximation are valid. The reaction rate coefficients and thermodynamic parameters have been calculated by incorporating a comprehensive group additive framework. A microkinetic model for the pyrolysis of methyl esters with a carbon number of up to 19 has been generated using this tool. It is validated by comparing calculated and experimental yields of the pyrolysis of methyl decanoate and novel rapeseed methyl ester pyrolysis data in the temperature range from 800 to 1100 K and methyl ester partial pressure range from 1 × 10^?3 to 1 × 10^?2 MPa. This modeling frame work allows to not only assess the use of methyl ester mixtures as potential feedstock for olefin production but also their effect as blend‐in or trace impurity. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4309–4322, 2015     

Do ‘green’ buildings have better indoor environments? New evidence

A post-occupancy evaluation (POE) of 12 green and 12 conventional office buildings across Canada and the northern United States was conducted. Occupants (N = 2545) completed an online questionnaire related to environmental satisfaction, job satisfaction and organizational commitment, health and well-being, environmental attitudes, and commuting. In each building on-site physical measurements at a sample of workstations (N= 974) were taken, including: thermal conditions, air quality, acoustics, lighting, workstation size, ceiling height, window access and shading, and surface finishes. Green buildings exhibited superior performance compared with similar conventional buildings. Better outcomes included: environmental satisfaction, satisfaction with thermal conditions, satisfaction with the view to the outside, aesthetic appearance, less disturbance from heating, ventilation and air-conditioning (HVAC) noise, workplace image, night-time sleep quality, mood, physical symptoms, and reduced number of airborne particulates. A variety of physical features led to improved occupant outcomes across all buildings, including: conditions associated with speech privacy, lower background noise levels, higher light levels, greater access to windows, conditions associated with thermal comfort, and fewer airborne particulates. Green building rating systems might benefit from further attention in several areas, including: credits related to acoustic performance, a greater focus on reducing airborne particulates, enhanced support for the interdisciplinary design process and development of POE protocols.

Il a été mené une évaluation après occupation (POE) de 12 immeubles de bureaux verts et 12 immeubles de bureaux classiques répartis à travers le Canada et le nord des Etats-Unis. Les occupants (N?=?2545) ont rempli un questionnaire en ligne portant sur la satisfaction environnementale, la satisfaction au travail et l'implication organisationnelle, la santé et le bien-être, les attitudes environnementales, et les trajets réguliers. Dans chaque immeuble, des mesures physiques in situ sur un échantillon de postes de travail (N?=?974) ont été effectuées, comprenant : les conditions thermiques, la qualité de l'air, l'acoustique, l'éclairage, la taille des postes de travail, la hauteur de plafond, l'accès aux fenêtres et leur occultation, et les finitions de surface. Les bâtiments verts ont affiché des performances supérieures par rapport aux bâtiments classiques similaires. De meilleurs résultats ont été obtenus concernant la satisfaction environnementale, la satisfaction à l'égard des conditions thermiques, la satisfaction à l'égard de la vue sur l'extérieur, l'aspect esthétique, la diminution des perturbations liées aux bruits provenant du chauffage, de la ventilation et de la climatisation (CVC), l'image du lieu de travail, la qualité du sommeil nocturne, l'humeur, les symptômes physiques, et la réduction du nombre de particules en suspension dans l'air. Différentes caractéristiques physiques ont conduit à une amélioration des résultats pour les occupants dans tous les immeubles, concernant notamment les conditions liées à la confidentialité des conversations, les niveaux inférieurs de bruit de fond, les niveaux de luminosité plus élevés, l'accès accru aux fenêtres, les conditions associées au confort thermique, et le nombre moindre de particules en suspension dans l'air. Les systèmes de notation des bâtiments verts pourraient bénéficier d'une plus grande attention apportée à plusieurs domaines, s'agissant en particulier des crédits relatifs aux performances acoustiques, d'un accent accru sur la réduction des particules en suspension dans l'air, d'un soutien renforcé en faveur du processus de conception interdisciplinaire et du développement de protocoles POE.

Mots clés: performances des bâtiments, bilan environnemental, bâtiments verts, environnement intérieur, Leadership in Energy and Environmental Design (LEED), satisfaction des occupants, évaluation après occupation