Global Sensitivity Analysis in Life-Cycle Assessment of Early-Stage Technology using Detailed Process Simulation: Application to Dialkylimidazolium Ionic Liquid Production.

The ability to assess the environmental performance of early-stage technologies at production scale is critical for sustainable process development. This paper presents a systematic methodology for uncertainty quantification in life-cycle assessment (LCA) of such technologies using global sensitivity analysis (GSA) coupled with a detailed process simulator and LCA database. This methodology accounts for uncertainty in both the background and foreground life-cycle inventories, and is enabled by lumping multiple background flows, either downstream or upstream of the foreground processes, in order to reduce the number of factors in the sensitivity analysis. A case study comparing the life-cycle impacts of two dialkylimidazolium ionic liquids is conducted to illustrate the methodology. Failure to account for the foreground process uncertainty alongside the background uncertainty is shown to underestimate the predicted variance of the end-point environmental impacts by a factor of two. Variance-based GSA furthermore reveals that only few foreground and background uncertain parameters contribute significantly to the total variance in the end-point environmental impacts. As well as emphasizing the need to account for foreground uncertainties in LCA of early-stage technologies, these results illustrate how GSA can empower more reliable decision-making in LCA.

A digital platform for the design of patient-centric supply chains.

Chimeric Antigen Receptor (CAR) T cell therapies have received increasing attention, showing promising results in the treatment of acute lymphoblastic leukaemia and aggressive B cell lymphoma. Unlike typical cancer treatments, autologous CAR T cell therapies are patient-specific; this makes them a unique therapeutic to manufacture and distribute. In this work, we focus on the development of a computer modelling tool to assist the design and assessment of supply chain structures that can reliably and cost-efficiently deliver autologous CAR T cell therapies. We focus on four demand scales (200, 500, 1000 and 2000 patients annually) and we assess the tool's capabilities with respect to the design of responsive supply chain candidate solutions while minimising cost.

[Interdisciplinarity and critical care in emergency medicine]. / Interdisciplinarité et urgences vitales en médecine d'urgence.

Cardiorespiratory arrest, stroke and severe trauma have serious consequences if untreated with strict procedures in a timely manner. This temporal imperative implies the implementation of a succession of actions coordinated by healthcare providers with diverse expertise, and operating according to known, mastered and trained standards of care. Simple and clear communication principles ensure the consistency and fluidity of these actions. Competent and inclusive leadership promotes the achievement of set objectives and allows the team to adapt to demanding or unforeseen situations. Interdisciplinarity as it is practiced in the emergency setting for critical pathways such as those mentioned, then takes on its full meaning.

L'arrêt cardiorespiratoire, l'accident vasculaire cérébral et le traumatisé grave sont grevés de lourdes conséquences s'ils ne sont pas traités avec des procédures strictes dans des délais adéquats. Cet impératif temporel implique la mise en œuvre d'une succession d'actions coordonnées par des intervenants à l'expertise diverse et opérant selon des standards de soins connus, maîtrisés et entraînés. Des principes de communication simples et clairs assurent la cohérence et la fluidité de ces actions. Un leadership, compétent et inclusif, favorise l'atteinte des objectifs fixés et permet l'adaptation de l'équipe aux situations exigeantes ou imprévues. L'interdisciplinarité telle qu'elle est pratiquée pour ces filières de soins critiques prend alors tout son sens.

[Ultrasound's tips and pitfalls]. / Pièges et astuces de l'échographie Clinique.

Ultrasound represents the 5th pillar of the clinical examination. There is no doubt about his improvement of diagnostic performance on the bedside examination. The POCUS (Point Of Care UltraSound) provides a binary answer to a simple question : «â€…Does this suprapubic mass correspond to an overdistended bladder ? Is this cervical nodule a lymph node ? ¼. But be careful, as with any exam, you must know the main technical and interpretation difficulties. This article gives some tips, mainly for beginners, and shows some pitfalls that could lead to misinterpretation through ignorance.

L'échographie représente aujourd'hui le 5e pilier de l'examen clinique. Il ne fait plus de doute que cet outil améliore la performance diagnostique du praticien au lit du malade. Le POCUS (Point-of-care ultrasonography) permet de répondre de manière binaire à une question simple : «â€…Est-ce que cette masse sus-pubienne correspond à un globe vésical ? Est-ce que ce nodule cervical est un ganglion ? ¼ Mais attention, comme pour tout examen, il faut en connaître les principales difficultés techniques et d'interprétation. Cet article donne quelques trucs, principalement pour les débutants, et indique certains pièges qui, par méconnaissance, peuvent entraîner une mauvaise interprétation.

The Influence of Initiator Concentration on Selected Properties of Thermosensitive Poly(Acrylamide-co-2-Acrylamido-2-Methyl-1-Propanesulfonic Acid) Microparticles.

Thermosensitive polymers PS1-PS5 were synthesized via the surfactant free precipitation polymerization (SFPP) using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA), and potassium persulfate (KPS) at 70 °C in aqueous environment. The effect of KPS concentrations on particle size and lower critical temperature solution (LCST) was examined by dynamic light scattering (DLS). The conductivity in the course of the synthesis and during cooling were investigated. The structural studies were performed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), H nuclear magnetic resonance (1H NMR), thermogravimetric analysis (TGA/DTA) and powder X-ray diffraction (PXRD). ATR-FTIR, 1H NMR and PXRD data confirmed the polymeric nature of the material. TGA/DTA curves demonstrated thermal stability up to approx. 160 °C. The effect of temperature on the hydrodynamic diameter (HD) and zeta potential (ZP) were evaluated by dynamic light scattering (DLS) and electrophoretic mobility (EM) in 18-45 °C range. The LCST values were between 30 and 34 °C. HD and polydispersity index (PDI) of aqueous dispersions of the synthesized polymers PS1-PS5 at 18 °C were found to be 226 ± 35 nm (PDI = 0.42 ± 0.04), 299 ± 145 nm (PDI = 0.49 ± 0.29), 389 ± 39 nm (PDI = 0.28 ± 0.07), 584 ± 75 nm (PDI = 0.44 ± 0.06), and 271 ± 50.00 nm (PDI = 0.26 ± 0.14), respectively. At 18 °C the ZPs of synthesized polymers suspensions were -13.14 ± 2.85 mV, -19.52 ± 2.86 mV, -7.73 ± 2.76 mV, -7.99 ± 1.70 mV, and -9.05 ± 2.60 mV for PS1-PS5, respectively. We found that the initiator concentration influences the physicochemical properties of products including the size of polymeric particles and the LCST.

Bacterial Nanocellulose and Its Surface Modification by Glycidyl Methacrylate and Ethylene Glycol Dimethacrylate. Incorporation of Vancomycin and Ciprofloxacin.

Among nanocelluloses, bacterial nanocellulose (BNC) has proven to be a promising candidate in a range of biomedical applications, from topical wound dressings to tissue-engineering scaffolds. Chemical modifications and incorporation of bioactive molecules have been obtained, further increasing the potential of BNC. This study describes the incorporation of vancomycin and ciprofloxacin in BNC and in modified BNC to afford bioactive BNCs suitable for topical wound dressings and tissue-engineering scaffolds. BNC was modified by grafting glycidylmethacrylate (GMA) and further cross-linking with ethylene glycol dimethacrylate (EGDMA) with the formation of stable C-C bonds though a radical Fenton-type process that involves generation of cellulose carbon centred radicals scavenged by methacrylate structures. The average molar substitution degree MS (MS = methacrylate residue per glucose unit, measured by Fourier transform infrared (FT-IR) analysis) can be modulated in a large range from 0.1 up to 3. BNC-GMA, BNC-EGDMA and BNC-GMA-EGDMA maintain the hydrogel status until MS reaches the value of 1. The mechanical stress resistance increase of BNC-GMA and BNC-GMA-EGDMA of MS around 0.8 with respect to BNC suggests that they can be preferred to BNC for tissue-engineering scaffolds in cases where the resistance plays a crucial role. BNC, BNC-GMA, BNC-EGDMA and BNC-GMA-EGDMA were loaded with vancomycin (VC) and ciprofloxacin (CP) and submitted to release experiments. BNC-GMA-EGDMA of high substitution degree (0.7-1) hold up to 50 percentage of the loaded vancomycin and ciprofloxacin amount, suggesting that they can be further investigated for long-term antimicrobial activity. Furthermore, they were not colonized by Staphylococcus aureus (S.A.) and Klebsiella pneumonia (K.P.). Grafting and cross-linking BNC modification emerges from our results as a good choice to improve the BNC potential in biomedical applications like topical wound dressings and tissue-engineering scaffolds.

The potential of quantitative models to improve microalgae photosynthetic efficiency.

The massive increase in carbon dioxide concentration in the atmosphere driven by human activities is causing huge negative consequences and new sustainable sources of energy, food and materials are highly needed. Algae are unicellular photosynthetic microorganisms that can provide a highly strategic contribution to this challenge as alternative source of biomass to complement crops cultivation. Algae industrial cultures are commonly limited by light availability, and biomass accumulation is strongly dependent on their photon-to-biomass conversion efficiency. Investigation of algae photosynthetic metabolism is thus strategic for the generation of more efficient strains with higher productivity. Algae are cultivated at industrial scale in conditions highly different from the natural niches they adapted to and strains development efforts must fully consider the seminal influence on productivity of regulatory mechanism of photosynthesis as well as of cultivation parameters like cells concentration, light distribution in the culture, mixing, nutrients and carbon dioxide availability. In this review we will focus in particular on how mathematical models can account for the complex influence of all environmental parameters and can be exploited for development of improved algae strains.

Effect of the Electron Transport Layer on the Interfacial Energy Barriers and Lifetime of R2R Printed Organic Solar Cell Modules.

Understanding the phenomena at interfaces is crucial for producing efficient and stable flexible organic solar cell modules. Minimized energy barriers enable efficient charge transfer, and good adhesion allows mechanical and environmental stability and thus increased lifetime. We utilize here the inverted organic solar module stack and standard photoactive materials (a blend of poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester) to study the interfaces in a pilot scale large-area roll-to-roll (R2R) process. The results show that the adhesion and work function of the zinc oxide nanoparticle based electron transport layer can be controlled in the R2R process, which allows optimization of performance and lifetime. Plasma treatment of zinc oxide (ZnO) nanoparticles and encapsulation-induced oxygen trapping will increase the absolute value of the ZnO work function, resulting in energy barriers and an S-shaped IV curve. However, light soaking will decrease the zinc oxide work function close to the original value and the S-shape can be recovered, leading to power conversion efficiencies above 3%. We present also an electrical simulation, which supports the results. Finally, we study the effect of plasma treatment in more detail and show that we can effectively remove the organic ligands around the ZnO nanoparticles from the printed layer in a R2R process, resulting in increased adhesion. This postprinting plasma treatment increases the lifetime of the R2R printed modules significantly with modules retaining 80% of their efficiency for ∼3000 h in accelerated conditions. Without plasma treatment, this efficiency level is reached in less than 1000 h.

A mathematical model to guide genetic engineering of photosynthetic metabolism.

The optimization of algae biomass productivity in industrial cultivation systems requires genetic improvement of wild type strains isolated from nature. One of the main factors affecting algae productivity is their efficiency in converting light into chemical energy and this has been a major target of recent genetic efforts. However, photosynthetic productivity in algae cultures depends on many environmental parameters, making the identification of advantageous genotypes complex and the achievement of concrete improvements slow. In this work, we developed a mathematical model to describe the key factors influencing algae photosynthetic productivity in a photobioreactor, using experimental measurements for the WT strain of Nannochloropsis gaditana. The model was then exploited to predict the effect of potential genetic modifications on algae performances in an industrial context, showing the ability to predict the productivity of mutants with specific photosynthetic phenotypes. These results show that a quantitative model can be exploited to identify the genetic modifications with the highest impact on productivity taking into full account the complex influence of environmental conditions, efficiently guiding engineering efforts.

Semi-empirical modeling of microalgae photosynthesis in different acclimation states - Application to N. gaditana.

The development of mathematical models capable of accurate predictions of the photosynthetic productivity of microalgae under variable light conditions is paramount to the development of large-scale production systems. The process of photoacclimation is particularly important in outdoor cultivation systems, whereby seasonal variation of the light irradiance can greatly influence microalgae growth. This paper presents a dynamic model that captures the effect of photoacclimation on the photosynthetic production. It builds upon an existing semi-empirical model describing the processes of photoproduction, photoregulation and photoinhibition via the introduction of acclimation rules for key parameters. The model is calibrated against a dataset comprising pulsed amplitude modulation fluorescence, photosynthesis rate, and antenna size measurements for the microalga Nannochloropsis gaditana in several acclimation states. It is shown that the calibrated model is capable of accurate predictions of fluorescence and respirometry data, both in interpolation and in extrapolation.

Correction: High-Fidelity Modelling Methodology of Light-Limited Photosynthetic Production in Microalgae.

[This corrects the article DOI: 10.1371/journal.pone.0152387.].

High-Fidelity Modelling Methodology of Light-Limited Photosynthetic Production in Microalgae.

Reliable quantitative description of light-limited growth in microalgae is key to improving the design and operation of industrial production systems. This article shows how the capability to predict photosynthetic processes can benefit from a synergy between mathematical modelling and lab-scale experiments using systematic design of experiment techniques. A model of chlorophyll fluorescence developed by the authors [Nikolaou et al., J Biotechnol 194:91-99, 2015] is used as starting point, whereby the representation of non-photochemical-quenching (NPQ) process is refined for biological consistency. This model spans multiple time scales ranging from milliseconds to hours, thus calling for a combination of various experimental techniques in order to arrive at a sufficiently rich data set and determine statistically meaningful estimates for the model parameters. The methodology is demonstrated for the microalga Nannochloropsis gaditana by combining pulse amplitude modulation (PAM) fluorescence, photosynthesis rate and antenna size measurements. The results show that the calibrated model is capable of accurate quantitative predictions under a wide range of transient light conditions. Moreover, this work provides an experimental validation of the link between fluorescence and photosynthesis-irradiance (PI) curves which had been theoricized.

The effect of donor content on the efficiency of P3HT:PCBM bilayers: optical and photocurrent spectral data analyses.

State-of-the-art organic solar cells mostly rely on bulk-heterojunction architectures, where the photoactive layer is cast from a solution containing both the electron donor and acceptor components and subsequently annealed. An alternative route for device preparation is the sequential deposition of the two components using "orthogonal" solvents. The morphology of sequentially deposited bilayers has been extensively studied, but the interplay between optical and electrical properties and its influence on device efficiency is still unclear. Here we present a study of poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) bilayers with variable P3HT content, including also a standard bulk-heterojunction device for comparison. Measured optical absorption, external quantum efficieny (EQE), and internal quantum efficiency (IQE) data are analysed and interpreted with the aid of numerical models. In agreement with other studies, our results suggest substantial intermixing between the PCBM and P3HT component, regardless of the P3HT content. In the bulk heterojunction and the bilayer devices with an active layer thickness of 100 nm or less, our best fits to both the optical and optoelectronic data highlight a concentration inversion, with an accumulation of PCBM on the anode side. Through the numerical analysis of device performance at short-circuit, we also find that exciton diffusion toward the P3HT:PCBM interface and geminate recombination can be the main IQE loss factors. Additional losses, attributed to bimolecular electron-hole recombination, are also observed upon increasing the P3HT content.

A model of chlorophyll fluorescence in microalgae integrating photoproduction, photoinhibition and photoregulation.

This paper presents a mathematical model capable of quantitative prediction of the state of the photosynthetic apparatus of microalgae in terms of their open, closed and damaged reaction centers under variable light conditions. This model combines the processes of photoproduction and photoinhibition in the Han model with a novel mathematical representation of photoprotective mechanisms, including qE-quenching and qI-quenching. For calibration and validation purposes, the model can be used to simulate fluorescence fluxes, such as those measured in PAM fluorometry, as well as classical fluorescence indexes. A calibration is carried out for the microalga Nannochloropsis gaditana, whereby 9 out of the 13 model parameters are estimated with good statistical significance using the realized, minimal and maximal fluorescence fluxes measured from a typical PAM protocol. The model is further validated by considering a more challenging PAM protocol alternating periods of intense light and dark, showing a good ability to provide quantitative predictions of the fluorescence fluxes even though it was calibrated for a different and somewhat simpler PAM protocol. A promising application of the model is for the prediction of PI-response curves based on PAM fluorometry, together with the long-term prospect of combining it with hydrodynamic and light attenuation models for high-fidelity simulation and optimization of full-scale microalgae production systems.

Numerical simulation of photocurrent generation in bilayer organic solar cells: Comparison of master equation and kinetic Monte Carlo approaches.

Numerical approaches can provide useful information about the microscopic processes underlying photocurrent generation in organic solar cells (OSCs). Among them, the Kinetic Monte Carlo (KMC) method is conceptually the simplest, but computationally the most intensive. A less demanding alternative is potentially represented by so-called Master Equation (ME) approaches, where the equations describing particle dynamics rely on the mean-field approximation and their solution is attained numerically, rather than stochastically. The description of charge separation dynamics, the treatment of electrostatic interactions and numerical stability are some of the key issues which have prevented the application of these methods to OSC modelling, despite of their successes in the study of charge transport in disordered system. Here we describe a three-dimensional ME approach to photocurrent generation in OSCs which attempts to deal with these issues. The reliability of the proposed method is tested against reference KMC simulations on bilayer heterojunction solar cells. Comparison of the current-voltage curves shows that the model well approximates the exact result for most devices. The largest deviations in current densities are mainly due to the adoption of the mean-field approximation for electrostatic interactions. The presence of deep traps, in devices characterized by strong energy disorder, may also affect result quality. Comparison of the simulation times reveals that the ME algorithm runs, on the average, one order of magnitude faster than KMC.

Oxidative stress, body fat composition, and endocrine status in pre- and postmenopausal women.

OBJECTIVE: To evaluate the role of menopause on the regional composition and distribution of fat in women and eventual correlations with the oxidative state. DESIGN: In this observational clinical investigation, 90 women (classified for menopause status according to Stages of Reproductive Aging Workshop criteria) were evaluated for body mass composition and fat distribution by dual-energy x-ray absorptiometry and for oxidative status by determination of serum hydroperoxide levels and residual antioxidant activity. RESULTS: Total body fat mass increases significantly in postmenopause (P < 0.05) by 22% in comparison with premenopause, with specific increases in fat deposition at the level of trunk (abdominal and visceral) (P < 0.001) and arms (P < 0.001). Concomitantly, the antioxidant status increases significantly (P < 0.001) by 17%. When data were adjusted for age by analysis of covariance, statistical significance disappeared for the increase in fat mass, but it was retained for antioxidant status (P < 0.05). Both antioxidant status and hydroperoxide level increased with trunk fat mass, as shown by linear correlation analysis (r = 0.46, P < 0.001 and r = 0.26, P < 0.05, respectively). CONCLUSIONS: The results of our investigation demonstrate that fat content increases in the upper part of the body (trunk and arms) in postmenopause and that age is the main determinant of this increase. During the comparison of premenopausal and postmenopausal women, we also detected a significant increase in antioxidant status. Apparently this change is mainly related to menopausal endocrine and fat changes.