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A little acid can accelerate a wide range of chemical reactions. The advent of chiral phosphoric acid derivatives has been useful for biasing these reactions toward just one of two mirror-image products. For the most part, though, these chiral catalysts have interacted with basic sites such as carbonyl groups. Tsuji et al. now extend asymmetric acid catalysis to simple carbon-carbon double bonds. Their custom imidodiphosphate forms a pocket that orients olefins to achieve mainly intramolecular alkoxylation on just one face after protonation. Science , this issue p. 1501 A chiral phosphoric acid derivative can catalytically control the stereochemistry of olefin hydroalkoxylation. The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Brønsted acidic sites of appropriate strength can protonate olefins and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral Brønsted acid catalysts to activate imines and carbonyl compounds, mimicking these enzymes to protonate simple olefins that then engage in asymmetric catalytic reactions has remained a substantial synthetic challenge. Here, we show that a class of confined and strong chiral Brønsted acids enables the catalytic asymmetric intramolecular hydroalkoxylation of unbiased olefins. The methodology gives rapid access to biologically active 1,1-disubstituted tetrahydrofurans, including (–)-Boivinianin A.

Durability is the most important factor for evaluating the service life of concrete, and the chemical attack of sulfate is an important factor affecting the durability of concrete. In this paper, fly ash, slag, metakaolin and silica fume were used as mineral admixtures to explore their impact on sulfate chemical attack, and the chemical attack mechanism of sulphate was deeply analyzed, the results showed that: the incorporation of fly ash, slag, and silica fume effectively improves the sulfate-resistant chemical attack capacity of concrete. The concrete was chemically attacked 30d in sulfate solution, which will increased its compressive strength and quality, it was mainly due to the secondary hydration reaction of fly ash and slag, part Ca (OH)2 reacted with Na2SO4 solution to generate gypsum and ettringite, and made the internal structure of concrete more compact. As the age of sulfate chemical attack increases, the ettringite expands with water, and causes concrete to be expanded or peeled. Silica fume mainly provides more active SiO2 for the secondary hydration reaction, consumes more Ca (OH)2, and reduces the formation of ettringite.

Methods for the synthesis and functionalization of amines are intrinsically important to a variety of chemical applications. We present a general carbon-hydrogen bond activation process that combines readily available aliphatic amines and the feedstock gas carbon monoxide to form synthetically versatile value-added amide products. The operationally straightforward palladium-catalyzed process exploits a distinct reaction pathway, wherein a sterically hindered carboxylate ligand orchestrates an amine attack on a palladium anhydride to transform aliphatic amines into β-lactams. The reaction is successful with a wide range of secondary amines and can be used as a late-stage functionalization tactic to deliver advanced, highly functionalized amine products of utility for pharmaceutical research and other areas.

This review focuses on recent advances in concrete durability using graphene oxide (GO) as a nanomaterial additive, with a goal to fill the gap between concrete technology, chemical interactions, and concrete durability, whilst providing insights for the adaptation of GO as an additive in concrete construction. An overview of concrete durability applications, key durability failure mechanisms of concrete, transportation mechanisms, chemical reactions involved in compromising durability, and the chemical alterations within a concrete system are discussed to understand how they impact the overall durability of concrete. The existing literature on the durability and chemical resistance of GO-reinforced concrete and mortar was reviewed and summarized. The impacts of nano-additives on the durability of concrete and its mechanisms are thoroughly discussed, particularly focusing on GO as the primary nanomaterial and its impact on durability. Finally, research gaps, future recommendations, and challenges related to the durability of mass-scale GO applications are presented.

Recent studies have recognised highly oxygenated organic molecules (HOMs) in the atmosphere as important in the formation of secondary organic aerosol (SOA). A large number of studies have focused on HOM formation from oxidation of biogenically emitted monoterpenes. However, HOM formation from anthropogenic vapours has so far received much less attention. Previous studies have identified the importance of aromatic volatile organic compounds (VOCs) for SOA formation. In this study, we investigated several aromatic compounds, benzene (C6H6), toluene (C7H8), and naphthalene (C10H8), for their potential to form HOMs upon reaction with hydroxyl radicals (OH). We performed flow tube experiments with all three VOCs and focused in detail on benzene HOM formation in the Jülich Plant Atmosphere Chamber (JPAC). In JPAC, we also investigated the response of HOMs to NOx and seed aerosol. Using a nitrate-based chemical ionisation mass spectrometer (CI-APi-TOF), we observed the formation of HOMs in the flow reactor oxidation of benzene from the first OH attack. However, in the oxidation of toluene and naphthalene, which were injected at lower concentrations, multi-generation OH oxidation seemed to impact the HOM composition. We tested this in more detail for the benzene system in the JPAC, which allowed for studying longer residence times. The results showed that the apparent molar benzene HOM yield under our experimental conditions varied from 4.1 % to 14.0 %, with a strong dependence on the OH concentration, indicating that the majority of observed HOMs formed through multiple OH-oxidation steps. The composition of the identified HOMs in the mass spectrum also supported this hypothesis. By injecting only phenol into the chamber, we found that phenol oxidation cannot be solely responsible for the observed HOMs in benzene experiments. When NOx was added to the chamber, HOM composition changed and many oxygenated nitrogen-containing products were observed in CI-APi-TOF. Upon seed aerosol injection, the HOM loss rate was higher than predicted by irreversible condensation, suggesting that some undetected oxygenated intermediates also condensed onto seed aerosol, which is in line with the hypothesis that some of the HOMs were formed in multi-generation OH oxidation. Based on our results, we conclude that HOM yield and composition in aromatic systems strongly depend on OH and VOC concentration and more studies are needed to fully understand this effect on the formation of HOMs and, consequently, SOA. We also suggest that the dependence of HOM yield on chamber conditions may explain part of the variability in SOA yields reported in the literature and strongly advise monitoring HOMs in future SOA studies.

Key Points Covalent DNA–protein crosslinks (DPCs) are highly toxic DNA lesions that are induced by widely used classes of chemotherapeutics and also by various external and endogenous agents. DPCs consist of three distinct components, which are harnessed by distinct repair mechanisms as a starting point for repair. Tyrosyl-DNA phosphodiesterases directly hydrolyse the covalent bond between protein and DNA at DPCs. Nuclease-dependent repair by the MRE11–RAD50–NBS1 (MRN) complex targets the DNA component of DPCs. Proteolytic repair by the spartan (SPRTN)/weak suppressor of SMT3 protein 1 (Wss1) protease family degrades the protein component of DPCs. Inhibition of DPC repair pathways offers novel therapeutic opportunities for anticancer combination therapies. Covalent DNA–protein crosslinks (DPCs) are induced by various compounds, which include widely used anticancer drugs, and are highly cytotoxic. Recent studies have revealed the mechanisms and the regulation of DPC repair pathways and suggest that components of these pathways can serve as targets for anticancer therapies. Covalent DNA–protein crosslinks (DPCs, also known as protein adducts) of topoisomerases and other proteins with DNA are highly toxic DNA lesions. Of note, chemical agents that induce DPCs include widely used classes of chemotherapeutics. Their bulkiness blocks virtually every chromatin-based process and makes them intractable for repair by canonical repair pathways. Distinct DPC repair pathways employ unique points of attack and are crucial for the maintenance of genome stability. Tyrosyl-DNA phosphodiesterases (TDPs) directly hydrolyse the covalent linkage between protein and DNA. The MRE11–RAD50–NBS1 (MRN) nuclease complex targets the DNA component of DPCs, excising the fragment affected by the lesion, whereas proteases of the spartan (SPRTN)/weak suppressor of SMT3 protein 1 (Wss1) family target the protein component. Loss of these pathways renders cells sensitive to DPC-inducing chemotherapeutics, and DPC repair pathways are thus attractive targets for combination cancer therapy.

Presence of aggressive chemicals in ground and groundwater can deteriorate concrete foundations or its reinforcements. Concrete codes require preventive measures to assure durability of concrete foundations which is based on geochemistry information of the site. Construction in the city of Rasht, in the Iranian Caspian coast, is fast growing often without sufficient geochemistry data for residential buildings. The later may pose risk of chemical attacks on concrete foundations. To resolve this shortcoming, this study aimed at investigating geochemistry of ground and groundwater from the upper 10 m which can serve as a preliminary guideline for shallow foundation constructions in the city. The database for this study included previous geochemical investigations from 50 boreholes in the city as well as boring eleven test pits at various locations along with soil and groundwater geochemistry tests. The geochemistry experiments included measurement of sulfate, chloride, organic matter, as well as pH in soil and groundwater. Geochemistry of ground and groundwater in the city mostly fell within permissible limits set by a local concrete code. Based on current study, service environment for shallow concrete foundations in the city was categorized in a moderate class; hence, durability requirements from the same local concrete code were emphasized.

Geopolymers are alternative materials to portland cement, obtained by alkaline activation of aluminosilicates. They exhibit excellent properties and a wide range of potential applications in the field of civil engineering. Several natural aluminosilicates and industrial by-products can be used for geopolymer synthesis, but a lot of starting materials have the disadvantage of poor reactivity and low strength development. This paper presents a comprehensive review of the main methods used to alter the reactivity of aluminosilicate materials for geopolymer synthesis, as reported recently in the literature. The methods consist of mechanical, thermal, physical separation and chemical activation, of which mechanical activation is the most commonly employed technique. The reactivity of the activated aluminosilicate materials is mainly related to the activation method and the treatment parameters. Chemical activation by alkaline fusion is a promising method allowing preparation of one-part geopolymer materials, an alternative class of geopolymeric binders. However, the resulting alkaline-fused geopolymer products are vulnerable to attack by excessive alkalis.

In recent years, the search for biological methods to avoid the application of chemical products in agriculture has led to investigating the use of biopolymers-based materials. Among the tested biomaterials, the best results were obtained from those based on the biopolymer chitosan (CHT). CHT, available in large quantities from the deacetylation of chitin, has multiple advantages: it is safe, inexpensive and can be easily associated with other compounds to achieve better performance. In this review, we have summarized the latest researches of the application of CHT on plant productivity, plant protection against the attack of pathogens and extension of the commercial life of detached fruits.

Significant progress has been made in understanding the cues involved in the host and mate seeking behaviors of spotted wing drosophila, Drosophila suzukii (Matsumura). This insect pest has been discovered in many fruit growing regions around the world since 2008. Unlike closely related Drosophila species, D. suzukii attacks fresh fruit and has become a severe pest of soft fruits including strawberry, cherry, blackberry, blueberry, raspberry, and may pose a threat to grapes. Prior to 2008, little was known about the courtship and host-seeking behaviors or chemical ecology of this pest. Since then, researchers have gained a better understanding of D. suzukii attraction to specific odors from fermentation, yeast, fruit, and leaf sources, and the visual cues that elicit long-range attraction. Several compounds have also been identified that elicit aversive behaviors in adult D. suzukii flies. Progress has been made in identifying the constituent compounds from these odor sources that elicit D. suzukii antennal responses in electrophysiological assays. Commercial lures based on food volatiles have been developed to attract D. suzukii using these components and efforts have been made to improve trap designs for monitoring this pest under field conditions. However, current food-based lures and trap technologies are not expected to be specific to D. suzukii and thus capture large numbers of non-target drosophilids. Attractive and aversive compounds are being evaluated for monitoring, mass trapping, and for the development of attract-and-kill and push-pull techniques to manage D. suzukii populations. This review outlines presently available research on the chemical ecology of D. suzukii and discusses areas for future research.