Thermal conductivity and heat capacity of solid AgCl under pressure

Using the transient hot-wire method, measurements were made for solid AgCl of both the thermal conductivity, , and the heat capacity per unit volume, c _p, where is the mass density. Measurements were made in the temperature range 100 to 400 K, and at pressures up to 2 GPa. c _p(P, T) could be adequately described if the acoustic modes were represented by a Debye model and the optic modes by an Einstein model. Analysis of (T) showed that only the acoustic modes needed to be taken into account up to 300 K, but that the optic modes were increasingly effective in carrying heat at higher temperatures. (P) was adequately described by the Lawson formula, but not by the Leibfried-Schlömann formula, to which it is formally equivalent. Agreement with experiment could be achieved by two different modifications of the Leibfried-Schlömann formula, although neither has a firm theoretical basis.     

Photoswitchable Superabsorbency Based on Nanocellulose Aerogels

Chemical vapor deposition of a thin titanium dioxide (TiO₂) film on lightweight native nanocellulose aerogels offers a novel type of functional material that shows photoswitching between water‐superabsorbent and water‐repellent states. Cellulose nanofibrils (diameters in the range of 5–20 nm) with native crystalline internal structures are topical due to their attractive mechanical properties, and they have become relevant for applications due to the recent progress in the methods of their preparation. Highly porous, nanocellulose aerogels are here first formed by freeze‐drying from the corresponding aqueous gels. Well‐defined, nearly conformal TiO₂ coatings with thicknesses of about 7 nm are prepared by chemical vapor deposition on the aerogel skeleton. Weighing shows that such TiO₂‐coated aerogel specimens essentially do not absorb water upon immersion, which is also evidenced by a high contact angle for water of 140° on the surface. Upon UV illumination, they absorb water 16 times their own weight and show a vanishing contact angle on the surface, allowing them to be denoted as superabsorbents. Recovery of the original absorption and wetting properties occurs upon storage in the dark. That the cellulose nanofibrils spontaneously aggregate into porous sheets of different length scales during freeze‐drying is relevant: in the water‐repellent state they may stabilize air pockets, as evidenced by a high contact angle, in the superabsorbent state they facilitate rapid water‐spreading into the aerogel cavities by capillary effects. The TiO₂‐coated nanocellulose aerogels also show photo‐oxidative decomposition, i.e., photocatalytic activity, which, in combination with the porous structure, is interesting for applications such as water purification. It is expected that the present dynamic, externally controlled, organic/inorganic aerogels will open technically relevant approaches for various applications.     

Theoretical Spectroscopy of the NiII Intermediate States in the Catalytic Cycle and the Activation of [NiFe] Hydrogenases

[NiFe] hydrogenases catalyze the reversible oxidation of dihydrogen. The corresponding catalytic cycle involves a formidable number of redox states of the Ni‐Fe active site; these can be distinguished experimentally by the IR stretching frequencies of their CN and CO ligands coordinated to iron. These spectroscopic fingerprints serve as sensitive probes for the intrinsic electronic structure of the metal core and, indirectly, for the structural composition of the active site. In this study, density functional theory (DFT) was used to calculate vibrational frequencies, by focusing on the EPR‐silent intermediate states that contain divalent metal centers. By using the well‐characterized Ni‐C and Ni‐B states as references, we identified candidates for the Ni‐SI_r, Ni‐SI_a, and Ni‐R states by matching the predicted relative frequency shifts with experimental results. The Ni‐SI_r and Ni‐SI_a states feature a water molecule loosely bound to nickel and a formally vacant bridge. Both states are connected to each other through protonation equilibria; that is, in the Ni‐SI_a state one of the terminal thiolates is protonated, whereas in Ni‐SI_r this thiolate is unprotonated. For the reduced Ni‐R state two feasible models emerged: in one, H₂ coordinates side‐on to nickel, and the second features a hydride bridge and a protonated thiolate. The Ni‐SU state remains elusive as no unequivocal correspondence between the experimental data and calculated frequencies of the models was found, thus indicating that a larger structural rearrangement might occur upon reduction from Ni‐A to Ni‐SU and that the bridging ligand might dissociate.     

Experimental study of a mechanically ventilated double-skin façade with venetian sun-shading device: A full-scale investigation in controlled environment

The aim of this article is to present results of an experimental campaign performed on a full-scale facility provided with a double-skin façade. The behaviour of this architectural concept is tested under controlled climatic conditions. A summer case is scrutinised under different configurations: variation of the airflow through the double-skin façade and different angle of the solar shading device. This paper describes the experimental conditions, as well the test facility and the tested façade element. The results show the temperatures of the test cell and the façade and how they depend on the climatic conditions and the sun-shading device blade angles. One objective of this research was to measure and provide extensive data set detailing air and surface temperatures on the double-skin façade, together with airflow rates and air velocities. The experiments are fully described so that the results can be used for the validation of numerical models dealing with ventilated double-skin façades with venetian sun-shading device.     

New interventions in cerebrovascular disease: the role of thrombolytic therapy and balloon angioplasty

The use of thrombolytic agents (plasminogen activators) in the early moments of ischemic stroke to achieve recanalization and potential neurologic improvement has been actively studied over the past 10 years. In the same period, endovascular techniques for cerebral revascularization have evolved significantly. Recent phase III studies, following angiography-based phase I and II studies of plasminogen activators in stroke, have described evidence of clinical benefit and contributors to morbidity (i.e., symptomatic hemorrhage) and mortality that limit the applicability of this approach. The limited formalized experience with percutaneous transluminal balloon angioplasty and stent placement in the carotid artery and cerebral circulation has given rise to concerns about the safety and appropriateness of the procedures in this territory. However, several prospective series support the feasibility of well-designed clinical trials.     

Supporting perspective taking across chasms of thinking: Do real-time analytics hold the key?

International Journal of Computer-Supported Collaborative Learning -