Synthesis and Structural Characterization of CSH-Phases in the Range of C/S = 0.41 - 1.66 at Temperatures of the Tobermorite Xonotlite Crossover

Calcium-Silicate-Hydrate-phases (CSH-phases) are important binding agents of building materials. The synthesis of CSH phases and their structural characterization was done to investigate the crystallization in dependence of an increasing CaO/SiO2 ratio (C/S ratios) from 0.41 up to 1.66 at temperatures in the crossover region of tobermorite to xonotlite (180℃ and 230℃). Parallel runs with the same C/S ratio but on the one hand with constant mass of quartz and variation of lime and on the other hand under reverse conditions (constant mass of lime but variable amounts of quartz) were performed at both temperatures. The aim was to clarify the connections of crystallization mechanism and kinetics of phase formation with structure, crystallinity and morphology of the CSH’s in the mentioned C/S ratio for both temperatures in the tobermorite-xonotlite crossover region. The parallel experiments with different mass ratios of the educts are important to study the influence of time evaluation of supersaturation within the solution under the peculiarities of the retrograde solubility of lime but accelerated solubility of quartz. The products were characterized by XRD, SEM/EDX, FTIR and 29Si MAS NMR spectroscopy (using the Q-site nomenclature [1]). The experiments could clarify some important connections of crystallization process and the reaction pathway

Investigation of the Transition Reaction of Tobermorite to Xonotlite under Influence of Additives

The objective of the present work was to investigate the transition reaction of the calcium silicate hydrate tobermorite into xonotlite under influence of additives. Tobermorite is the main binding agent in steam hardened building materials and the appearance of xonotlite indicates the progress of hardening and an overcuring of the material. Hydrothermal experiments under addition of sucrose, calcium formate and calcium chloride dihydrate to the main components quartz and lime were done using temperatures of 220°C and a reaction time of 40.5 h. All experiments were performed with powders as well as with pressed educts. The products of all syntheses were analyzed with XRD, SEM/EDX and FTIR. The references as well as the syntheses with calcium chloride dihydrate led to the formation of 11 Å tobermorite and xonotlite. The former showed the best results and even synthesis with pressed educts and calcium chloride dihydrate revealed an accelerating effect of the additive. In contrast syntheses with sucrose had the worst reactivity and led to the formation of calcite beside the CSH-phase scawtite. The additive calcium formate was only slightly oppressing the crystallization of tobermorite and favouring the formation of xonotlite. Syntheses with pressed pellets and sucrose or calcium formate showed generally worse results

Zeolite Synthesis under Insertion of Silica Rich Filtration Residues from Industrial Wastewater Reconditioning

Zeolite synthesis was studied using two silica rich filtration residues (FR 1 and FR 2) as Si-source and sodium aluminate in a direct synthesis at 60°C at strong alkaline conditions (8 M - 16 M NaOH). In addition to these one-pot syntheses, a two-step process was investigated. Here, an alkaline digestion of FR at 60°C was followed by gel precipitation with sodium aluminate and gel crystallization under usual conditions of 80°C - 90°C. The results show that the substitution of chemical reagent sodium silicate by a waste material like FR as Si-source is possible but requires fine tuning of the reaction conditions as zeolite crystallization is a process under kinetic control. The solubility behaviour and impurities of the inserted filtration residues strongly influenced the course of reaction. Thus zeolites like hydrosodalite or intermediate zeolite between cancrinite and sodalite, or zeolite NaA or Z-21 in cocrystallization with hydrosodalite could be observed in the one pot syntheses already in a short time interval between 1 - 4 h depending on the alkalinity. The two step process yield to zeolites NaA and NaX in very good quality. The reaction process of FR in both reaction methods was characterized by chemical analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy as well as scanning electron microscopy. Surface area and water content of selected products were further characterized by the BET-method and by thermogravimetry. Summing up the results, we can show that zeolite formation from filtration residues is possible by several reaction procedures as model cases for a re-use of industrial waste materials. Beside the importance for environmental protection, the reactions are of interest for zeolite chemistry as the re-use of FR is possible under economically conditions of low energy consumption at 60°C and short reaction periods.DF

Synthesis of aryl α,α-difluoroethyl thioethers a novel structure motif in organic chemistry, and extending to aryl α,α-difluoro oxyethers

The authors thank the Marie Curie ITN programme for Funding (AR).A method for the preparation of aryl α,α-difluoroethyl thioethers (ArSCF2CH3) is reported and the synthesis approach is extended to aryl alpha,alpha-difluoroethyl oxygen ethers. Selected building blocks are further elaborated in cross-coupling reactions and are incorporated into analogues of established trifluoromethyl ether drugs. Conformations are explored and log P studies of these motifs indicate that they are significantly more polar than their trifluoromethyl ether analogues rendering them attractive for bioactives discovery.PostprintPostprintPeer reviewe

The decision to move : response times, neuronal circuits and sensory memory in a simple vertebrate

All animals use sensory systems to monitor external events and have to decide whether to move. Response times are long and variable compared to reflexes, and fast escape movements. The complexity of adult vertebrate brains makes it difficult to trace the neuronal circuits underlying basic decisions to move. To simplify the problem, we investigate the nervous system and responses of hatchling frog tadpoles which swim when their skin is stimulated. Studying the neuron-by-neuron pathway from sensory to hindbrain neurons, where the decision to swim is made, has revealed two simple pathways generating excitation which sums to threshold in these neurons to initiate swimming. The direct pathway leads to short, and reliable delays like an escape response. The other includes a population of sensory processing neurons which extend firing to introduce noise and delay into responses. These neurons provide a brief, sensory memory of the stimulus, that allows tadpoles to integrate stimuli occurring within a second or so of each other. We relate these findings to other studies and conclude that sensory memory makes a fundamental contribution to simple decisions and is present in the brainstem of a basic vertebrate at a surprisingly early stage in development.PostprintPeer reviewe

A simple decision to move in response to touch reveals basic sensory memory and mechanisms for variable response times

Many motor responses to sensory input, like locomotion or eye movements, are much slower than reflexes. Can simpler animals provide fundamental answers about the cellular mechanisms for motor decisions? Can we observe the ‘accumulation’ of excitation to threshold proposed to underlie decision making elsewhere? We explore how somatosensory touch stimulation leads to the decision to swim in hatchling Xenopus tadpoles. Delays measured to swimming in behaving and immobilized tadpoles are long and variable. Activity in their extensively studied sensory and sensory pathway neurons is too short-lived to explain these response delays. Instead, whole-cell recordings from the hindbrain reticulospinal neurons that drive swimming show these receive prolonged, variable synaptic excitation lasting for nearly a second following a brief stimulus. They fire and initiate swimming when this excitation reaches threshold. Analysis of the summation of excitation requires us to propose extended firing in currently undefined presynaptic hindbrain neurons. Simple models show that a small excitatory recurrent-network inserted in the sensory pathway can mimic this process. We suggest that such a network may generate slow, variable summation of excitation to threshold. This excitation provides a simple memory of the sensory stimulus. It allows temporal and spatial integration of sensory inputs and explains the long, variable delays to swimming. The process resembles the ‘accumulation’ of excitation proposed for cortical circuits in mammals. We conclude that fundamental elements of sensory memory and decision making are present in the brainstem at a surprisingly early stage in development

Individual rules for trail pattern formation in Argentine ants (Linepithema humile)

We studied the formation of trail patterns by Argentine ants exploring an empty arena. Using a novel imaging and analysis technique we estimated pheromone concentrations at all spatial positions in the experimental arena and at different times. Then we derived the response function of individual ants to pheromone concentrations by looking at correlations between concentrations and changes in speed or direction of the ants. Ants were found to turn in response to local pheromone concentrations, while their speed was largely unaffected by these concentrations. Ants did not integrate pheromone concentrations over time, with the concentration of pheromone in a 1 cm radius in front of the ant determining the turning angle. The response to pheromone was found to follow a Weber's Law, such that the difference between quantities of pheromone on the two sides of the ant divided by their sum determines the magnitude of the turning angle. This proportional response is in apparent contradiction with the well-established non-linear choice function used in the literature to model the results of binary bridge experiments in ant colonies (Deneubourg et al. 1990). However, agent based simulations implementing the Weber's Law response function led to the formation of trails and reproduced results reported in the literature. We show analytically that a sigmoidal response, analogous to that in the classical Deneubourg model for collective decision making, can be derived from the individual Weber-type response to pheromone concentrations that we have established in our experiments when directional noise around the preferred direction of movement of the ants is assumed.Comment: final version, 9 figures, submitted to Plos Computational Biology (accepted

European patch test results with audit allergens as candidates for inclusion in the European Baseline Series, 2019/20:Joint results of the ESSCA(A) and the EBSB working groups of the ESCD, and the GEIDAC(C)

Background In 2019, a number of allergens (haptens), henceforth, "the audit allergens," were considered as potential additions to the European Baseline Series (EBS), namely, sodium metabisulfite, 2-bromo-2-nitropropane-1,3-diol, diazolidinyl urea, imidazolidinyl urea, Compositae mix II (2.5% or 5% pet), linalool hydroperoxides (lin-OOH), limonene hydroperoxides (lim-OOH), benzisothiazolinone (BIT), octylisothiazolinone (OIT), decyl glucoside, and lauryl glucoside; Evernia furfuracea (tree moss), was additionally tested by some departments as well. Objectives To collect further data on patch test reactivity and clinical relevance of the audit allergens in consecutive patients across Europe. Methods Patch test data covering the audit allergens in 2019 and 2020 were collected by those departments of the European Surveillance System on Contact Allergies testing these, as well as further collaborators from the EBS working group of the European Society of Contact Dermatitis (ESCD), and the Spanish Grupo Espanol de Investigacion en Dermatitis de Contacto y Alergia Cutanea. As patch test outcome, reactions between day (D) 3 and D5 were considered. Results Altogether n = 12 403 patients were tested with any of the audit allergen. Positive reactions were most common to lin-OOH 1% pet. (8.74% [95%CI: 8.14-9.37%]), followed by lin-OOH 0.5% pet., and lim-OOH 0.3% pet (5.41% [95% CI: 4.95-5.89%]). Beyond these terpene hydroperoxides, BIT 0.1% pet. was the second most common allergen with 4.72% (95% CI: 4.2-5.28%), followed by sodium metabisulfite 1% pet. (3.75% [95%CI: 3.32-4.23%]) and Compositae mix 5% pet. (2.31% [95% CI: 1.84-2.87%]). For some allergens, clinical relevance was frequently difficult to ascertain. Conclusions Despite many positive patch test reactions, it remains controversial whether lin- and lim-OOH should be tested routinely, while at least the two preservatives BIT and sodium metabisulfite appear suitable. The present results are a basis for further discussion and ultimately decision on their implementation into routine testing among the ESCD members

Patch test results with the European baseline series, 2019/20-Joint European results of the ESSCA and the EBS working groups of the ESCD, and the GEIDAC

BACKGROUND Continual analyses of patch test results with the European baseline series (EBS) serve both contact allergy surveillance and auditing the value of included allergens. OBJECTIVES To present results of current EBS patch testing, obtained in 53 departments in 13 European countries during 2019 and 2020. METHODS Anonymised or pseudonymised individual data, and partly aggregated data on demographic/clinical characteristics and patch test rest results with the EBS were prospectively collected and centrally pooled and analysed. RESULTS In 2019 and 2020, 22581 patients were patch tested with the EBS. Sensitization to nickel remained most common (19.8 (19.2-20.4)% positivity (95% confidence interval)). Fragrance mix I and Myroxylon pereirae yielded very similar results with 6.80 (6.43-7.19)% and 6.62 (6.25-7.00)% positivity, respectively. Formaldehyde at 2% aq. yielded almost one percentage point more positive reactions than 1% concentration (2.49 (2.16-2.85)% vs. 1.59 (1.33-1.88)); methylchloroisothiazolinone/methylisothiazolinone (MCI/MI) and MI alone up to around 5% positives. Among the new additions, propolis was most commonly positive (3.48 (3.16-3.82)%), followed by 2-hydroxyethyl methacrylate (2.32 (2.0-2.68)%). CONCLUSIONS Ongoing surveillance on the prevalence of contact sensitization contributes to an up-to-date baseline series containing the most frequent and/or relevant contact sensitizers for routine patch testing in Europe. This article is protected by copyright. All rights reserved

Multi-scale Inference of Interaction Rules in Animal Groups Using Bayesian Model Selection

Inference of interaction rules of animals moving in groups usually relies on an analysis of large scale system behaviour. Models are tuned through repeated simulation until they match the observed behaviour. More recent work has used the fine scale motions of animals to validate and fit the rules of interaction of animals in groups. Here, we use a Bayesian methodology to compare a variety of models to the collective motion of glass prawns (Paratya australiensis). We show that these exhibit a stereotypical ‘phase transition’, whereby an increase in density leads to the onset of collective motion in one direction. We fit models to this data, which range from: a mean-field model where all prawns interact globally; to a spatial Markovian model where prawns are self-propelled particles influenced only by the current positions and directions of their neighbours; up to non-Markovian models where prawns have ‘memory’ of previous interactions, integrating their experiences over time when deciding to change behaviour. We show that the mean-field model fits the large scale behaviour of the system, but does not capture fine scale rules of interaction, which are primarily mediated by physical contact. Conversely, the Markovian self-propelled particle model captures the fine scale rules of interaction but fails to reproduce global dynamics. The most sophisticated model, the non-Markovian model, provides a good match to the data at both the fine scale and in terms of reproducing global dynamics. We conclude that prawns' movements are influenced by not just the current direction of nearby conspecifics, but also those encountered in the recent past. Given the simplicity of prawns as a study system our research suggests that self-propelled particle models of collective motion should, if they are to be realistic at multiple biological scales, include memory of previous interactions and other non-Markovian effects