A Mechanistic Perspective on the Mechanochemical Method To Reduce Carbonyl Groups with Stainless Steel and Water

Mechanochemistry through high-speed ball milling has become an increasingly popular method for performing organic transformations. This newfound interest in high-speed ball milling is in part driven by the benefit of performing reactions in the absence of solvent. Mechanochemical reactions are often conducted in stainless-steel vials with stainless-steel balls. Since stainless steel is made of several readily oxidizable metals (Fe, Cr, and Ni), reduction reactions using water as a hydrogen source were explored using a temperature-controlled mixer mill. Mechanistic studies suggest that the reduction proceeds via a single electron transfer (SET) pathway, with iron and nickel being essential components for the reaction.     

Intrinsically Chiral Twist-Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase

The front cover artwork is provided by Dr Rebecca Walker of the Liquid Crystals Group at the University of Aberdeen. The image is a cartoon depiction of the formation of the heliconical chiral twist-bend nematic phase (N*_TB) from its constituent bent molecules. The presence of a single enantiomer of the chiral, lactate-based liquid crystal dimers biases the formation of helices with only one handedness, unlike in the conventional N_TB phase, observed for achiral molecules, for which the left- and right-handed helices are doubly degenerate. Read the full text of the Research Article at 10.1002/cphc.202200807 .     

Integrated approaches for reducing sample size for measurements of trace elemental impurities in plutonium by ICP-OES and ICP-MS

A novel microsphere adsorbent based upon carboxymethyl cellulose sodium/prussian blue composite loaded with Lanthanum(III) (CMC/PB-La) was successfully synthesized via electrostatic ejection device for removal of cesium from contaminated water, and characterized by FT-IR, SEM, EDX and XPS. Influencing factors to adsorption cesium were investigated, including solution pH, adsorbent dosage, contact time, initial concentration, temperature and competing ions. Linear Freundlich isotherm was fitted satisfactorily to the adsorption data, and the adsorption kinetic data was fitted well with pseudo-second-order model. Moreover, the results of γ-irradiation experiments indicate that CMC/PB-La has good radiation stability.     

Alkaline aqueous solution promoted debromination of 1,2 dibromo-fluorocarbons – A convenient method for electron deficient perfluorovinyl ethers

A facile and efficient base-mediated protocol for debromination of vic-dibromides in perfluoroalkyl(aryl) compounds in aqueous medium has been demonstrated. With mild reaction conditions, the developed strategy has a good substrate scope and electron-deficient olefin products were obtained in good yields. A mechanistic explanation of the debromination is offered with three key experimental observations: (1) the reactions are accelerated by the more electron-rich nucleophiles, (2) the reactions are promoted by the more electron poor vic-dibromides in perfluoroalkyl compounds, and (3) the nucleophilic side reaction is preventable. It is evident that the electronic factors strongly dictate vic-dibromides elimination to the perfluorovinyl ethers, which are the precursors for various perfluorinated polymers. The different reaction conditions were tested in implicit solvent (water) conditions, which helped to confirm the E2-like mechanism.     

Probing the Gaseous Structure of a β-Hairpin Peptide with H/D Exchange and Electron Capture Dissociation

An improved understanding of the extent to which native protein structure is retained upon transfer to the gas phase promises to enhance biological mass spectrometry, potentially streamlining workflows and providing fundamental insights into hydration effects. Here, we investigate the gaseous conformation of a model β-hairpin peptide using gas-phase hydrogen–deuterium (H/D) exchange with subsequent electron capture dissociation (ECD). Global gas-phase H/D exchange levels, and residue-specific exchange levels derived from ECD data, are compared among the wild type 16-residue peptide GB1p and several variants. High protection from H/D exchange observed for GB1p, but not for a truncated version, is consistent with the retention of secondary structure of GB1p in the gas phase or its refolding into some other compact structure. Four alanine mutants that destabilize the hairpin in solution show levels of protection similar to that of GB1p, suggesting collapse or (re)folding of these peptides upon transfer to the gas phase. These results offer a starting point from which to understand how a key secondary structural element, the β-hairpin, is affected by transfer to the gas phase. This work also demonstrates the utility of a much-needed addition to the tool set that is currently available for the investigation of the gaseous conformation of biomolecules, which can be employed in the future to better characterize gaseous proteins and protein complexes.

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Overlapping MALDI-Mass Spectrometry Imaging for In-Parallel MS and MS/MS Data Acquisition without Sacrificing Spatial Resolution

Metabolomics experiments require chemical identifications, often through MS/MS analysis. In mass spectrometry imaging (MSI), this necessitates running several serial tissue sections or using a multiplex data acquisition method. We have previously developed a multiplex MSI method to obtain MS and MS/MS data in a single experiment to acquire more chemical information in less data acquisition time. In this method, each raster step is composed of several spiral steps and each spiral step is used for a separate scan event (e.g., MS or MS/MS). One main limitation of this method is the loss of spatial resolution as the number of spiral steps increases, limiting its applicability for high-spatial resolution MSI. In this work, we demonstrate multiplex MS imaging is possible without sacrificing spatial resolution by the use of overlapping spiral steps, instead of spatially separated spiral steps as used in the previous work. Significant amounts of matrix and analytes are still left after multiple spectral acquisitions, especially with nanoparticle matrices, so that high quality MS and MS/MS data can be obtained on virtually the same tissue spot. This method was then applied to visualize metabolites and acquire their MS/MS spectra in maize leaf cross-sections at 10 μm spatial resolution.

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SDA 7: A modular and parallel implementation of the simulation of diffusional association software

The simulation of diffusional association (SDA) Brownian dynamics software package has been widely used in the study of biomacromolecular association. Initially developed to calculate bimolecular protein–protein association rate constants, it has since been extended to study electron transfer rates, to predict the structures of biomacromolecular complexes, to investigate the adsorption of proteins to inorganic surfaces, and to simulate the dynamics of large systems containing many biomacromolecular solutes, allowing the study of concentration‐dependent effects. These extensions have led to a number of divergent versions of the software. In this article, we report the development of the latest version of the software (SDA 7). This release was developed to consolidate the existing codes into a single framework, while improving the parallelization of the code to better exploit modern multicore shared memory computer architectures. It is built using a modular object‐oriented programming scheme, to allow for easy maintenance and extension of the software, and includes new features, such as adding flexible solute representations. We discuss a number of application examples, which describe some of the methods available in the release, and provide benchmarking data to demonstrate the parallel performance. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.     

A systematic study of rare gas atoms encapsulated in small fullerenes using dispersion corrected density functional theory

The most stable fullerene structures from C₂₀ to C₆₀ are chosen to study the energetics and geometrical consequences of encapsulating the rare gas elements He, Ne, or Ar inside the fullerene cage using dispersion corrected density functional theory. An exponential increase in stability is found with increasing number of carbon atoms. A similar exponential law is found for the volume expansion of the cage due to rare gas encapsulation with decreasing number of carbon atoms. We show that dispersion interactions become important with increasing size of the fullerene cage, where Van der Waals forces between the rare gas atom and the fullerene cage start to dominate over repulsive interactions. The smallest fullerenes where encapsulation of a rare gas element is energetically still favorable are He@C₄₈, Ne@C₅₂, and Ar@C₅₈. While dispersion interactions follow the trend Ar > Ne > He inside C₆₀ due to the trend in the rare gas dipole polarizabilities, repulsive forces become soon dominant with smaller cage size and we have a complete reversal for the energetics of rare gas encapsulation at C₅₀. © 2014 Wiley Periodicals, Inc.     

Ynamide Carbopalladation: A Flexible Route to Mono‐, Bi‐ and Tricyclic Azacycles

Bromoenynamides represent precursors to a diversity of azacycles by a cascade sequence of carbopalladation followed by cross‐coupling/electrocyclization, or reduction processes. Full details of our investigations into intramolecular ynamide carbopalladation are disclosed, which include the first examples of carbopalladation/cross‐coupling reactions using potassium organotrifluoroborate salts; and an understanding of factors influencing the success of these processes, including ring size, and the nature of the coupling partner. Additional mechanistic observations are reported, such as the isolation of triene intermediates for electrocyclization. A variety of hetero‐Diels–Alder reactions using the product heterocycles are also described, which provide insight into Diels–Alder regioselectivity.     

Divergent Gold(I)‐Catalyzed Skeletal Rearrangements of 1,7‐Enynes

The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n‐enynes (n=5–7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6‐enynes, readily accessible homologous 1,7‐enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all‐carbon 1,7‐enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7‐enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro‐anthracenes through a novel dehydrogenative Diels–Alder reaction.