Adsorption of PCE in alkali-activated materials analysed by fluorescence microscopy.

The realisation of high-performance concrete mixtures requires the use of superplasticizers to achieve a low water/binder ratio and thus high strengths. Polycarboxylate ethers (PCE) are mostly used as superplasticizers. The effectiveness of these superplasticizers depends on their chemical structure, the binders' alkaline environment and the ions present in the pore solution of the binder. In high alkaline systems like some alkali-activated materials no effective superplasticizer have been found yet. To unravel the compatibility of certain PCE to such a highly alkaline system a fluorescence microscopy approach was used. In first experiments, the adsorption of APEG (allyl ether) and MPEG (methacrylate) PCE on ground granulated blast furnace slag and fly ash was investigated varying the concentration of the activators. At a certain concentration, a complexation of the PCE can be recognised in fluorescence microscope. APEG shows a better stability compared to MPEG; this correlates with rheological investigations.

Growth of C-S-H phases on different metallic surfaces.

The influence of reinforcement, especially fibre reinforcement in ultra-high performance concrete is strongly dependent on the bonding (adhesive, shear and friction bond) between metallic surface and cementitious matrix. As usually straight fibres are used for fibre reinforcement and, thus, no significant mechanical bonding is existent, the adhesive bond is particularly important. Previous studies stated that the adhesive bonding behaviour between metallic materials and cementitious matrix strongly depends on the chemical composition of metallic alloys. Therefore, in order to address this topic, the present study investigates the growth of C-S-H phases on stainless steel and on cold drawn steel. This growth process was realised by a surface treatment of the metallic alloys using a synthetically manufactured Tricalciumsilicate (C3 S) powder diluted in water. After defined times of the C3 S treatment the process is stopped to get a time dependent growing behaviour of the cementitious phases. Light microscopy as well as scanning electron microscopy was used in order to investigate the surfaces following the application of the C3 S. The results reveal that the growth of C-S-H phases is more dependent on the metallic surface and its topography than on the alloy composition.

Corrosion inhibition in acidic environments: key interfacial insights with photoelectron spectroscopy.

In many engineering scenarios, surface-active organic species are added to acidic solutions to inhibit the corrosion of metallic components. Given suitable selection, such corrosion inhibitors are highly effective, preventing significant degradation even in highly aggressive environments. Nevertheless, there are still considerable gaps in fundamental knowledge of corrosion inhibitor functionality, severely restricting rational development. Here, we demonstrate the capability of X-ray photoelectron spectroscopy (XPS), supported by ab initio modelling, for revealing key details of inhibited substrates. Attention is focussed on the corrosion inhibition of carbon steel through the addition of an exemplar imidazoline-based corrosion inhibitor (OMID) to aqueous solutions of both HCl and H2SO4. Most notably, it is demonstrated that interfacial chemistry varies with the identity of the acid. High resolution Fe 2p, O 1s, N 1s, and Cl 2p XPS spectra, acquired from well-inhibited carbon steel in 1 M HCl, show that there are two different singly protonated OMID species bound directly to the metallic carbon steel substrate. In sharp contrast, in 0.01 M H2SO4, OMID adsorbs onto an ultra-thin surface film, composed primarily of a ferric sulfate (Fe2(SO4)3)-like phase. Such insight is essential to efforts to develop a mechanistic description of corrosion inhibitor functionality, as well as knowledge-based identification of next generation corrosion inhibitors.

Unexpected Retroaldol-Aldol Reaction during O-Alkylation of Hydroxylated Vince Lactam Derivatives.

The unexpected retroaldol-aldol reaction during O-alkylation of a ß-hydroxy lactam was found to be highly dependent on the temperature and shows a remarkable solvent effect. In DMF, O-alkylation is faster than retroaldol-aldol rearrangement giving exclusively products with retention of configuration. In THF, O-alkylation is slower than rearrangement, giving selectively products with inversion of stereochemistry. In DMSO, a retroaldol reaction followed by fast intramolecular proton transfer occurs to give the ring-opened aldehyde.

Potential of Fe-Mn-Al-Ni Shape Memory Alloys for Internal Prestressing of Ultra-High Performance Concrete.

Prestressing of concrete is a commonly used technique in civil engineering to achieve long spans, reduced structural thicknesses, and resource savings. However, in terms of application, complex tensioning devices are necessary, and prestress losses due to shrinkage and creep of the concrete are unfavourable in terms of sustainability. In this work, a prestressing method using novel Fe-Mn-Al-Ni shape memory alloy rebars as a tensioning system in UHPC is investigated. A generated stress of about 130 MPa was measured for the shape memory alloy rebars. For the application in UHPC, the rebars are prestrained prior to the manufacturing process of the concrete samples. After sufficient hardening of the concrete, the specimens are heated inside an oven to activate the shape memory effect and, thus, to introduce the prestress into the surrounding UHPC. It is clearly shown that an improvement in maximum flexural strength and rigidity is achieved due to the thermal activation of the shape memory alloy rebars compared to non-activated rebars. Future research will have to focus on the design of the shape memory alloy rebars in relation to construction applications and the investigation of the long-term performance of the prestressing system.

Bonding Behaviour of Steel Fibres in UHPFRC Based on Alkali-Activated Slag.

The mechanical performance of fibre-reinforced ultra-high-performance concrete based on alkali-activated slag was investigated, concentrating on the use of steel fibres. The flexural strength is slightly higher compared to the UHPC based on Ordinary Portland Cement (OPC) as the binder. Correlating the flexural strength test with multiple fibre-pullout tests, an increase in the bonding behaviour at the interfacial-transition zone of the AAM-UHPC was found compared to the OPC-UHPC. Microstructural investigations on the fibres after storage in an artificial pore solution and a potassium waterglass indicated a dissolution of the metallic surface. This occurred more strongly with the potassium waterglass, which was used as an activator solution in the case of the AAM-UHPC. From this, it can be assumed that the stronger bond results from this initial etching for steel fibres in the AAM-UHPC compared to the OPC-UHPC. The difference in the bond strength of both fibre types, the brass-coated steel fibres and the stainless-steel fibres, was rather low for the AAM-UHPC compared to the OPC-UHPC.

Identification of novel allosteric modulators for the G-protein coupled US28 receptor of human cytomegalovirus.

The highly constitutively active G-protein coupled receptor US28 of human cytomegalovirus (HCMV) is an interesting pharmacological target because of its implication on viral dissemination, cardiovascular diseases and tumorigenesis. We found that dihydroisoquinolinone and tetrahydroisoquinoline scaffolds may be promising lead structures for novel US28 allosteric inverse agonists. These scaffolds were rapidly synthesized by radical carboamination reactions followed by non-radical transformations. Our novel US28 allosteric modulators provide valuable scaffolds for further ligand optimization and may be helpful chemical tools to investigate molecular mechanisms of US28 constitutive signaling and its role in pathogenesis.

Durability Properties of Ultra-High Performance Lightweight Concrete (UHPLC) with Expanded Glass.

It is important to ensure the durability and safety of structures. In the case of newly developed materials that are outside the current rules, it is important to investigate all aspects of structural safety. The material studied in the following is a structural lightweight concrete with an ultra-high-performance matrix and expanded glass as a lightweight aggregate. The material, with a compressive strength of 60-100 MPa and a bulk density of 1.5-1.9 kg/dm3, showed high capillary porosities of 12 vol% (ultra-high-performance concretes (UHPC) < 5 vol%). Since the capillary porosity basically enables transport processes into the concrete, the material had to be examined more closely from the aspect of durability. Freeze-thaw resistance (68 g/m2) and chemical attack with sulfate at pH 3.5 for 12 weeks (16 g/m2) showed no increase in concrete corrosion. Targeted carbonation (0.53 mm/year0.5) and chloride penetration resistance (6.0 × 10-13 to 12.6 × 10-13 m2/s) also showed good results against reinforcement corrosion. The results show that most of the measured capillary pores resulted from the lightweight aggregate and were not all present as a pore system. Thus, the durability was only slightly affected and the concrete can be compared to an UHPC. Only the abrasion resistance showed an increased value (22,000 mm3/5000 mm2), which, however, only matters if the material is used as a screed.

Radical arylation of phenols, phenyl ethers, and furans.

Radical arylations of para-substituted phenols and phenyl ethers proceeded with good regioselectivity at the ortho position with respect to the hydroxy or alkoxy group. The reactions were conducted with arenediazonium salts as the aryl radical source, titanium(III) chloride as the reductant, and diluted hydrochloric acid as the solvent. Substituted biaryls were obtained from hydroxy- and alkoxy-substituted benzylamines, phenethylamines, and aromatic amino acids. The methodology described offers a fast, efficient, and cost-effective new access to diversely functionalized biphenyl alcohols and ethers. Free phenolic hydroxy groups, aromatic and aliphatic amines, as well as amino acid substructures, are well tolerated. Two examples for the applicability of the methodology are the partial synthesis of a beta-secretase inhibitor and the synthesis of a calcium-channel modulator.

Fluorescence Microscopic Investigations of the Retarding Effect of Superplasticizers in Cementitious Systems of UHPC.

The adsorption of superplasticizer molecules to particle surfaces in cementitious systems is a very important aspect for the desired liquefaction of pastes and concretes. This way, the comb shaped polymers shield attractive forces between the particles and induce a well-dispersed, homogeneous suspension. These admixtures allow the usage of fine fillers even in combination with low amounts of mixing water, and thus, are the basis for modern high performance concretes. However, the adsorption does not cause beneficial effects only: The polymer covered particle surfaces, especially clinker, are hindered to interact with water, thus hydration is retarded. This is the reason for lower early strength and is very disadvantageous for certain applications. Today it is known that the molecular structure of the polymers, for instance the chain length and charge density, affects the retardation strongly. The complexity and diversity of cementitious systems is the main reason why research in this field is quite empiric and time as well as cost intensive. To investigate the adsorption of superplasticizers in various systems in-situ, a fluorescence microscopic approach was applied: By staining the polymers with fluorescent dye they become localizable and the adsorption quantifiable. This work shows the influence of molecular structure to adsorption characteristic of different polymers and the correlation to the retarding effect of superplasticizers, especially concerning the presence of silica fume, which is indispensable for ultra-high performance concrete (UHPC).

Fluorescence Microscopy of Superplasticizers in Cementitious Systems: Applications and Challenges.

In addition to the desired plasticizing effect, superplasticizers used in high and ultra-high performance concretes (UHPC) influence the chemical system of the pastes and for example retardation of the cement hydration occurs. Thus, superplasticizers have to be chosen wisely for every material composition and application. To investigate the essential adsorption of these polymers to particle surfaces in-situ to overcome several practical challenges of superplasticizer research, fluorescence microscopy is useful. In order to make the superplasticizer polymers visible for this microscopic approach, they are stained with fluorescence dyes prior the experiment. In this work, the application of this method in terms of retardation and rheological properties of sample systems is presented. The hydration of tricalcium oxy silicate (C3S) in combination with different polycarboxylate ether superplasticizers is observed by fluorescence microscopy and calorimetry. Both methods can identify the retarding effect, depending on the superplasticizer's chemical composition. On the other hand, the influence of the superplasticizers on the slump of a ground granulated blast furnace slag/cement paste is correlated to fluorescence microscopic adsorption results. The prediction of the efficiency by microscopic adsorption analysis succeeds roughly. At last, the possibility of high-resolution imaging via confocal laser scanning microscopy is presented, which enables the detection of early hydrates and their interaction with the superplasticizers.

Effect of Fibre Material and Fibre Roughness on the Pullout Behaviour of Metallic Micro Fibres Embedded in UHPC.

The use of micro fibres in Ultra-High-Performance Concrete (UHPC) as reinforcement increases tensile strength and especially improves the post-cracking behaviour. Without using fibres, the dense structure of the concrete matrix results in a brittle failure upon loading. To counteract this behaviour by fibre reinforcement, an optimal bond between fibre and cementitious matrix is essential. For the composite properties not only the initial surfaces of the materials are important, but also the bonding characteristics at the interfacial transition zone (ITZ), which changes upon the joining of both materials. These changes are mainly induced by the bond of cementitious phases on the fibre. In the present work, three fibre types were used: steel fibres with brass coating, stainless-steel fibres as well as nickel-titanium shape memory alloys (SMA). SMA fibres have the ability of "remembering" an imprinted shape (referred to as shape memory effect), triggered by thermal activation or stress, principally providing for superior performance of the fibre-reinforced UHPC. However, previous studies have shown that NiTi-fibres have a much lower bond strength to the concrete matrix than steel fibres, eventually leading to a deterioration of the mechanical properties of the composite. Accordingly, the bond between both materials has to be improved. A possible strategy is to roughen the fibre surfaces to varying degrees by laser treatment. As a result, it can be shown that laser treated fibres are characterised by improved bonding behaviour. In order to determine the bond strength of straight, smooth fibres of different metal alloy compositions, the present study characterized multiple fibres in series with a Compact-Tension-Shear (CTS) device. For critical evaluation, results obtained by these tests are compared with the results of conventional testing procedures, i.e., bending tests employing concrete prisms with fibre reinforcements. The bond behaviour is compared with the results of the flexural strength of prisms (4 × 4 × 16 cm3) with fibre reinforcements.

Environmental Assessment of Ultra-High-Performance Concrete Using Carbon, Material, and Water Footprint.

There is a common understanding that the environmental impacts of construction materials should be significantly reduced. This article provides a comprehensive environmental assessment within Life Cycle Assessment (LCA) boundaries for Ultra-High-Performance Concrete (UHPC) in comparison with Conventional Concrete (CC), in terms of carbon, material, and water footprint. Environmental impacts are determined for the cradle-to-grave life cycle of the UHPC, considering precast and ready-mix concrete. The LCA shows that UHPC has higher environmental impacts per m³. When the functionality of UHPC is considered, at case study level, two design options of a bridge are tested, which use either totally CC (CC design) or CC enhanced with UHPC (UHPC design). The results show that the UHPC design could provide a reduction of 14%, 27%, and 43% of carbon, material, and water footprint, respectively.

Intermolecular radical carboaminohydroxylation of olefins with aryl diazonium salts and TEMPO.

Highly reactive aryl radicals can selectively be reacted with a broad variety of activated and nonactivated olefinic substrates in the presence of nitroxyl radicals. Direct recombination of the aryl radical and the nitroxide as well as telomerization of the olefin is successfully suppressed by the reaction conditions.

Regio- and Stereoselective Synthesis of Functionalized Cyclopentene Derivatives via Mizoroki-Heck Reactions.

Pd(0)-catalyzed Mizoroki-Heck alkenylations and arylations of protected aminocyclopentenes, prepared in a few steps from Vince lactam, afforded functionalized cyclopentenes in high yields and stereoselectivities. DFT calculations were performed to rationalize the high diastereoselectivities. Functionalized cyclopentene products were transformed into valuable chiral building blocks, such as cyclic γ-amino acids and carbocyclic nucleoside precursors.

Selective Synthesis of Spirooxindoles by an Intramolecular Heck-Mizoroki Reaction.

We report a highly diastereoselective synthesis of cyclopentene-spirooxindole derivatives via an intramolecular Heck-Mizoroki reaction using aryl bromides as precursors. The reactions were performed under dry conditions or in a DMF-water system. This protocol can be useful to introduce several functionalities to the aromatic nucleus of the spirooxindoles. DFT calculations were performed to rationalize the high antiselectivity. A functionalized spiroproduct was transformed into a cyclic amino acid derivative.

Selective alkylation of amines with alcohols by Cp*-iridium(III) half-sandwich complexes.

[Cp*Ir(Pro)Cl] (Pro = prolinato) was identified among a series of Cp*-iridium half-sandwich complexes as a highly reactive and selective catalyst for the alkylation of amines with alcohols. It is active under mild conditions in either toluene or water without the need for base or other additives, tolerates a wide range of alcohols and amines, and gives secondary amines in good to excellent isolated yields.