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While many photoresponsive metal‒organic frameworks (MOFs) have been reported to date, finding applications in several technologically relevant fields such as photocatalysis, sensors, and light‐emitting devices, significantly scarcer are the reports addressing the relationship between the MOFs emissive features and their crystalline domain size (i.e., micro‐ and nano‐sized materials). Herein, a valuable contribution is offered to this issue which consists of the use of reticular chemistry to prepare a Zr‐MOF featuring spatially separated tetracarboxylated‐functionalized perylenes as ligand. Single crystal X‐ray analysis of such Zr‐MOF revealed the formation of micro‐ and meso‐porous channels. The perylene‐based Zr‐MOF exhibited notable optoelectronic features, including a relatively small optical bandgap of 1.82 eV and emission features different from that of the constituting perylene ligand in the solid state. Additionally, local probe techniques are used to unveil the emission properties of isolated Zr‐MOF crystals. Space‐ and time‐resolved fluorescence studies revealed a strong dependence of the emissive features of the Zr‐MOF, both in terms of its intensity and lifetime, to the crystalline domain size. [ABSTRACT FROM AUTHOR]

One challenge for 3D printing is that the mortar must flow easily through the printer nozzle, and after printing, it must develop compressive strength fast and high enough to support the layers on it. This requires an exact and difficult control of the superplasticizer (SP) dosing. Nanocrystalline cellulose (CNC) has gained significant interest as a rheological modifier of mortar by interacting with the various cement components. This research studied the potential of nanocrystalline cellulose (CNC) as a mortar aid for 3D printing and its interactions with SPs. Interactions of a CNC and SP with cement suspensions were investigated by means of monitoring the effect on cement dispersion (by monitoring the particle chord length distributions in real time) and their impact on mortar mechanical properties. Although cement dispersion was increased by both CNC and SP, only CNC prevented cement agglomeration when shearing was reduced. Furthermore, combining SP and CNC led to faster development of compressive strength and increased compressive strength up to 30% compared to mortar that had undergone a one-day curing process. [ABSTRACT FROM AUTHOR]

Concrete-filled steel tubes (CFSTs) have attracted increasing interest in research during the last decade as a construction system that increases its performance due to the use of self-stressing concrete. The efficiency and confining pressure of this construction solution mainly depends on the expansion of the concrete mixture introduced into the steel tube. This study shows the importance of the correct design of the expansive mixes and the correct selection of components. The effect of three types of chemical admixtures (air-entrained, setting retarder, and hardening accelerator) commonly used in the ready-mixed concrete industry when added to a self-stressing concrete made with a K-type calcium sulfoaluminate–based expansion agent has been analyzed. This study showed that certain chemical admixtures, added in a fixed proportion, conditioned both the compressive strength and the magnitude and kinetics of the expansion in a restricted regime of the reference self-stressing concrete mix. The efficiency of the CFST and self-stressing concrete construction solution represented by the bond failure strength and the sliding load of the concrete core against the steel tube was influenced not by the compressive strength of the expansive concrete but by the degree of restrained expansion (confinement effect) achieved. In this research, an alternative test method for measuring expansion was proposed, which allows continuous recording of positive strains (expansions), eliminating the dependence on setting time for demolding; this method even allows the exact identification of the expansion beginning. Finally, it was proposed that the ettringite detectable by the X-ray diffraction (XRD) technique was not representative of the magnitude of expansion generated from K-type calcium sulfoaluminate expansive agents because the proportion of ettringite was not related to the expansion determined by the different test methods proposed. [ABSTRACT FROM AUTHOR]

The design, synthesis and evaluation of a subphthalocyanine-flipper (SubPc-Flipper) amphiphilic dyad is reported. This dyad combines two fluorophores that function in the visible region (420–800 nm) for the simultaneous sensing of both ordered and disordered lipidic membranes. The flipper probes part of the dyad possesses mechanosensitivity, long fluorescence lifetimes (τ = 3.5–5 ns) and selective staining of ordered membranes. On the other hand, subphthalocyanines (SubPc) are short-lifetime (τ = 1–2.5 ns) fluorophores that are insensitive to membrane tension. As a result of a Förster Resonance Energy Transfer (FRET) process, the dyad not only retains the mechanosensitivity of flippers but also demonstrates high selectivity and emission in different kinds of lipidic membranes. The dyad exhibits high emission and sensitivity to membrane tension (Δτ = 3.5 ns) when tested in giant unilamellar vesicles (GUVs) with different membrane orders. Overall, the results of this study represent a significant advancement in the applications of flippers and dyads in mechanobiology. [ABSTRACT FROM AUTHOR]

Ruthenium phthalocyanine (RuPcs) are multipurpose compounds characterized by their remarkable reactivity and photoelectronic properties, which yield a broad synthetic scope and easy derivatization at the axial position. However, RuPcs have been underexplored for use in organic thin‐film transistors (OTFTs), and therefore new studies are necessary to provide basic insight and a first approach in this new application. Herein, two novel RuPc derivatives, containing axial pyridine substituents with aliphatic chains (RuPc(CO)(PyrSiC6) (1) and RuPc(PyrSiC6)2 (2), were synthesized, characterized, and tested as the organic semiconductor in OTFTs. RuPc thin‐films were characterized by X‐ray diffraction (XRD), and atomic force microscopy (AFM) to assess film morphology and microstructure. 1 displayed comparable p‐type device performance to other phthalocyanine‐based OTFTs of similar design, with an average field effect mobility of 2.08×10−3 cm2 V−1 s−1 in air and 1.36×10−3 cm2 V−1 s−1 in nitrogen, and threshold voltages from −11 V to −20 V. 2 was found to be non‐functional as the semiconductor in the device architecture used, likely as a result of significant differences in thin‐film formation. The results of this work illustrate a promising starting point for future development of RuPc electronic devices, particularly in this new family of OTFTs. [ABSTRACT FROM AUTHOR]

In this study, different lightweight expanded glass aggregates (LEGAs) were produced from glass cullet and various carbonated wastes, through a thermal impact process. The effects of LEGA microstructure and morphology on both the adherence to the cement paste and the mechanical properties of mortars after 28 days of curing were studied. The properties of lightweight mortars made of either LEGAs or expanded clay aggregates were compared. The results demonstrated the feasibility of using LEGAs to produce glass lightweight aggregate mortar, with flexural and compressive strength values ranging from 5.5 to 8.2 MPa and from 28.1 to 47.6 MPa, respectively. The differences in mechanical properties were explained according to the microstructures of the fracture surfaces. Thus, arlite-type ceramic aggregates presented surface porosities that allowed mortar intrusion and the formation of an interconnected interface; although the surfaces of the vitreous aggregates were free from porosity due to their vitreous nature, the mortars obtained from different wastes presented compressive and flexural strengths in the range of lightweight mortars. [ABSTRACT FROM AUTHOR]

Contrary to sulfides, sulfoxides or sulfones, sulfoximines have been mostly neglected in the design of fluorescent probes until recently. In this study, we elaborate systematically on sulfoximine acceptors in fluorescent flipper probes. Fluorescent flippers have been introduced as mechanosensitive probes to image membrane order and tension. They consist of twisted dithienothiophene dimers with sulfide and sulfone bridges to produce the essential primary dipole of the coupled push‐pull system. The objective of this study was to replace the sulfone acceptor by a series of sulfoximines. This is intriguing as a synthetic challenge and worthwhile because the extra nitrogen substituent offers a variability that is attractive to understand and control the performance of the probes. The new sulfoximine flippers provide corroborative evidence for the importance of the primary dipole of the planarizable push‐pull probe. Partitioning into differently ordered membranes and positioning within these different membranes is shown to correlate directly and dramatically with fluorescence lifetimes and mechanosensitivity. Sufficient partitioning into ordered membranes is confirmed as particularly important to image membrane tension by probe compression in the ground state. Compared to the conventional sulfone homolog, the best sulfoximine flipper has more red‐shifted absorption and emission maxima, longer fluorescence lifetime in cell membranes, and larger difference in lifetime upon application of membrane tension. [ABSTRACT FROM AUTHOR]

Despite their growing popularity in biology to image membrane tension, central design principles of flipper probes have never been validated. Here we report that upon deletion of their primary dipole, from electron-poor and electron-rich dithienothiophenes, absorptions blue-shift, lifetimes shorten dramatically, and mechanosensitivity in cells vanishes not partially, but completely. [ABSTRACT FROM AUTHOR]

The water adducts of triacetone triperoxide (TATP) have been observed by using broadband rotational spectroscopy. This work opens a new way for the gas‐phase detection of this improvised explosive. The observed clusters exhibit unusual water dynamics and rarely observed multicenter interactions. TATP‐H2O is formed from the D3 symmetry conformer of TATP with water lying close to the C3 axis. Water rotation around this axis with a very low barrier gives rise to the rotational spectrum of a symmetric top. The main interaction of the monohydrate is a four‐center trifurcated donor Ow‐H⋅⋅⋅O hydrogen bond, not observed previously in the gas phase, reinforced by a weak four‐center trifurcated acceptor C−H⋅⋅⋅Ow interaction. Surprisingly, all structural signatures show the weakness of these interactions. The complex TATP‐(H2O)2 is formed from the monohydrated TATP by the self‐association of water. [ABSTRACT FROM AUTHOR]

A series of new ruthenium(II) vinyl complexes has been prepared incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalised with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low solubility of the perylene compounds was improved through the design of poly‐PEGylated (PEG=polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compounds on silica, vapours and gases could be detected in the solid state. The reaction of the complexes [Ru(CH=CH‐PerIm)Cl(CO)(py‐3PEG)(PPh3)2] and [Ru(CH=CH‐3PEG)Cl(CO)(py‐PerIm)(PPh3)2] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behaviour. The complexes were observed to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapours that are toxic to humans. [ABSTRACT FROM AUTHOR]

The cyclic depsipeptide cereulide toxin it is a very well‐known potassium electrogenic ionophore particularly sensitive to pancreatic beta cells. The mechanistic details of its specific activity are unknown. Here, we describe a series of synthetic substituted cereulide potassium ionophores that cause impressive selective activation of glucose‐induced insulin secretion in a constitutive manner in rat insulinoma INS1E cells. Our study demonstrates that the different electroneutral K+ transport mechanism exhibited by the anionic mutant depsipeptides when compared with classical electrogenic cereulides can have an important impact of pharmacological value on glucose‐stimulated insulin secretion. [ABSTRACT FROM AUTHOR]

The preparation of new monodisperse polycrystalline palladium nanoparticles uniformly distributed on the surface of polymers, by simply adding a palladium(ii) solution in water to the polymers, is described. The polymer supported palladium nanoparticles material was used as an efficient portable and reusable catalyst for the stereoselective semihydrogenation reaction of internal alkynes to (Z)-alkenes in green solvents. [ABSTRACT FROM AUTHOR]

We report the development of new fluorogenic silica nanomaterials that were able to generate fluorescence in the presence of vapours of triacetone triperoxide, TATP, an improvised explosive used in terrorist attacks. The materials worked in a vapour flow of TATP, giving a permanent and strongly fluorescent response. [ABSTRACT FROM AUTHOR]

The durability of an innovative self-healing micro-concrete in aggressive environments simulated by freeze-thaw cycles and salt spray test is studied. Tests are conducted on an ultra-high-strength reinforced micro-concrete that incorporates an autonomous self-healing mechanism based on the reaction of an epoxy compound enclosed within silica microcapsules and amine functionalised silica nanoparticles distributed within the cementitious matrix. The effect of aggressive environments is analysed in the self-healing micro-concrete and in a reference micro-concrete stored for 28 d in laboratory conditions after cracking, for crack widths of 150 and 300 μm. The results of capillary water absorption tests, complemented by electron microscopy analysis, confirm the enhanced durability of the autonomously self-healed material in both the freeze-thaw and the salt spray tests, as compared to the reference micro-concrete. In conclusion, the innovative self-healing mechanism is expected to increase the service life of structures in humid, cold climates and chloride-containing environments. [ABSTRACT FROM AUTHOR]

A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses. [ABSTRACT FROM AUTHOR]

We report the development of new chemical probes for cereulide, a toxic metabolite produced by specific strains of Bacillus cereus, through displacement of potassium cations from a preformed specific complex and a subsequent change in the fluorescence emission. For this purpose, we designed fluorescent probes for potassium cations that were suitable for displacement assays with cereulide from organic extracts. The fluorescence detection of natural cereulide in rice samples was achieved by using synthetic cereulide as a reference and a potassium fluorescent reporter, and this was found to be useful as a portable and fast method for the in situ detection of cereulide in food extracts. To study the fate of cereulide in live cells, we designed a procedure that was suitable for live-cell microscopy imaging of HeLa cells by comparing the cellular location of the potassium fluorogenic probe, which stained intracellular endolysosomes, in the absence and presence of cereulide; we concluded that in the presence of cereulide, the fluorescence of the probe was decreased because of complexation of the potassium ions by cereulide. [ABSTRACT FROM AUTHOR]

We have developed a new fluorogenic polymer capable of detecting the presence of mercury contamination in fish samples. The modified polymer emits blue light when irradiated with UV light proportional to the quantity of mercury, as MeHg+ or Hg2+, present in fish. The quantitative relation between the concentration of mercury in fish and the increase of fluorescence in the polymer in contact with fish samples was confirmed, giving rise to quick and reliable results in the measurements of the presence of mercury in fish using a portable fluorogenic polymeric probe. [ABSTRACT FROM AUTHOR]

This personal account describes our contribution to the design of selective fluorogenic probes for contaminants of high environmental impact. For this purpose, we have developed a new family of highly versatile fluorogenic reagents that were able to show large differences in their fluorescence in the presence of selected analytes. They were used in the preparation of fluorogenic probes for the detection of contaminants of high environmental impact which currently have no good solutions: phosphorylating agents, such as chemical weapons; methyl mercury(II); the cyanide anion; amino-acid metabolites, such as doping substances; and biogenic amine mimics, such as drugs of abuse and recreational drugs. The development of new materials for specific sensing was achieved by anchoring selected probes to silica nanomaterials, suitable for the selective detection of organic analytes in water for immediate application to toxicological or environmental purposes. [ABSTRACT FROM AUTHOR]

Calcium aluminate cement (CAC) is less commonly used as ordinary Portland cements (OPCs) for structural concrete, is relatively expensive, but may have certain advantages when used for solidification of wastes; it introduces rapid strength gain and has a higher resistance to chemical attack than OPC. However, the most widely identified degradation process suffered by CAC is the so-called conversion of hexagonal calcium aluminate hydrate to a cubic form. Mixes of CAC with silica fume (SF) or fly ash (FA) represent an interesting alternative for the stabilization of CAC hydrates, which might be attributed to a microstructure based mainly on aluminosilicates. This paper deals with the microstructure of cement pastes fabricated with binders of CAC–SF and CAC–FA, and their evolution over time. Mid infrared and near infrared spectroscopy have been used to assess the microstructure of these formulations. Microstructural characterization was completed by backscattering electron microscopy observation and microanalysis. [ABSTRACT FROM AUTHOR]

Fiber reinforcement of concrete is an effective technique of providing ductility to concrete, increasing its flexural residual strength while reducing its potential for cracking due to drying shrinkage. There are currently a wide variety of industrial fibers on the market. Recycled steel fibers (RSF) from tires could offer a viable substitute of industrialized fibers in a more sustainable and eco-friendly way. However, mistrust exists among users, based on fear that the recycling process will reduce the performance, coupled with the difficulty of characterization of the geometry of the RSF, as a consequence of the size variability introduced by the recycling process. This work compares the behavior of RSF from tires compared with industrialized steel or polypropylene fibers, evaluating the fresh state, compressive strength, flexural residual strength, and drying behavior. The concept of Equivalent Fiber Length (EFL) is also defined to help the statistical geometrical characterization of the RSF. A microstructural analysis was carried out to evaluate the integration of the fiber in the matrix, as well as the possible presence of contaminants. The conclusion is reached that the addition of RSF has a similar effect to that of industrialized fibers on concrete's properties when added at the same percentage. [ABSTRACT FROM AUTHOR]

Self-healing concrete has the potential to optimise traditional design approaches; however, commercial uptake requires the ability to harmonize against standardized frameworks. Within EU SARCOS COST Action, different interlaboratory tests were executed on different self-healing techniques. This paper reports on the evaluation of the effectiveness of proposed experimental methodologies suited for self-healing concrete with expansive mineral additions. Concrete prisms and discs with MgO-based healing agents were produced and precracked. Water absorption and water flow tests were executed over a healing period spanning 6 months to assess the sealing efficiency, and the crack width reduction with time was monitored. High variability was reported for both reference (REF) and healing-addition (ADD) series affecting the reproducibility of cracking. However, within each lab, the crack width creation was repeatable. ADD reported larger crack widths. The latter influenced the observed healing making direct comparisons across labs prone to errors. Water absorption tests highlighted were susceptible to application errors. Concurrently, the potential of water flow tests as a facile method for assessment of healing performance was shown across all labs. Overall, the importance of repeatability and reproducibility of testing methods is highlighted in providing a sound basis for incorporation of self-healing concepts in practical applications. [ABSTRACT FROM AUTHOR]

We describe the synthesis of fluorogenic arylureas and amides and their interaction with primary or secondary amines under air and light in organic-aqueous mixtures to give rise to a new class of persistent organic radicals, described on the basis of their electron paramagnetic resonance (EPR), as well as UV–vis, fluorescence, NMR, and quantum mechanics calculations, and their prospective use as multi-signal reporters in a smart label for fish freshness. [ABSTRACT FROM AUTHOR]

Cover Feature: Microwave Detection of Wet Triacetone Triperoxide (TATP): Non-Covalent Forces and Water Dynamics (Chem. Eur. J. 5/2021) Keywords: energetic materials; rotational spectroscopy; triacetone triperoxide; water adducts EN energetic materials rotational spectroscopy triacetone triperoxide water adducts 1481 1481 1 01/23/21 20210121 NES 210121 B Triacetone triperoxide (TATP) b is an explosive which, due to its ease of synthesis and difficulty of detection, is a common choice for the improvised explosive devices used by terrorists. Energetic materials, rotational spectroscopy, triacetone triperoxide, water adducts. [Extracted from the article]

Crystalline hydrophilic additives are increasingly used as efficient methods for reducing water permeability in concrete. Their effectiveness in hindering water penetration has been proven in different cementitious materials, although scarce information has been reported concerning their action mechanism. In the present work, the efficacy of a hydrophilic blended crystalline mix (Krystaline Add1) as a water-reducing additive has been confirmed. Furthermore, an extended study about how the presence of the additive influences both the fresh state and the hardened state properties is presented. Finally, characterization techniques such as Mercury Intrusion Porosimetry (MIP), X-ray Powder Diffraction (XRD) and Back-Scattered Scanning Electron Microscopy (BSEM) with Energy Dispersive X-ray analysis (EDAX) have been used for deducing the mechanism of the additive. No significant deleterious influence on the concrete properties due to the addition of the additive has been detected. In fact, the additive seems to have provided a positive influence on the concrete given that a slight reduction in the w/c ratio for similar consistency has been detected, with the subsequent improvement of the compressive strength values. Its effectiveness as a water permeability reducing additive has shown encouraging results having reduced the water permeability by approximately 50% during testing. The action mechanism of the studied additive seems to be related to hydration reactions in the presence of water, producing new solid amorphous phases in the concrete bulk. [ABSTRACT FROM AUTHOR]