X-ray absorption signatures of hydrogen-bond structure in water–alcohol solutions

Despite fundamental importance, the experimental characterization of the hydrogen bond network, particularly in multicomponent protic solutions, remains a challenge. Although recent work has experimentally validated that the oxygen K-edge X-ray absorption spectra is sensitive to local hydrogen bond patterns in pure water and aqueous alcohol solutions, the generality of this observation is unknown—as is the sensitivity to the electronic structure of the alcohol cosolvent. In this work, we investigate the electronic structure of water solvated alcohol model geometries using energy specific time-dependent density functional theory to calculate oxygen K-edge X-ray excitations. We find that the geometry of dangling hydrogen bonds in pure water is the main contributor to the pre-edge feature seen in the X-ray absorption spectra, agreeing with previous experimental and theoretical work. We then extend this result to solvated alcohol systems and observe a similar phenomenon, yet importantly, the increase of electron donation from alkyl chains to the alcohol OH group directly correlates to the strength of the core excitation on the dangling hydrogen bond model geometry. This trend arises from a stronger transition dipole moment due to electron localization on the OH group.     

Solvent‐free Liquid Crystals and Liquids from DNA

As DNA exhibits persistent structures with dimensions that exceed the range of their intermolecular forces, solid‐state DNA undergoes thermal degradation at elevated temperatures. Therefore, the realization of solvent‐free DNA fluids, including liquid crystals and liquids, still remains a significant challenge. To address this intriguing issue, we demonstrate that combining DNA with suitable cationic surfactants, followed by dehydration, can be a simple generic scheme for producing these solvent‐free DNA fluid systems. In the anhydrous smectic liquid crystalline phase, DNA sublayers are intercalated between aliphatic hydrocarbon sublayers. The lengths of the DNA and surfactant are found to be extremely important in tuning the physical properties of the fluids. Stable liquid‐crystalline and liquid phases are obtained in the ?20 °C to 200 °C temperature range without thermal degradation of the DNA. Thus, a new type of DNA‐based soft biomaterial has been achieved, which will promote the study and application of DNA in a much broader context.     

Allyl sulfides and α‐substituted acrylates as addition–fragmentation chain transfer agents for methacrylate polymer networks

The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition–fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth)acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well‐performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real‐time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 394–406     

Top-down synthesis of polyoxometalate-like sub-nanometer molybdenum-oxo clusters as high-performance electrocatalysts

The top-down fabrication of catalytically active molecular metal oxide anions, or polyoxometalates, is virtually unexplored, although these materials offer unique possibilities, for catalysis, energy conversion and storage. Here, we report a novel top-down route, which enables the scalable synthesis and deposition of sub-nanometer molybdenum-oxo clusters on electrically conductive mesoporous carbon. The new approach uses a unique redox-cycling process to convert crystalline Mo^IVO₂ particles into sub-nanometer molecular molybdenum-oxo clusters with a nuclearity of ∼1–20. The resulting molybdenum-oxo cluster/carbon composite shows outstanding, stable electrocatalytic performance for the oxygen reduction reaction with catalyst characteristics comparable to those of commercial Pt/C. This new material design could give access to a new class of highly reactive polyoxometalate-like metal oxo clusters as high-performance, earth abundant (electro-)catalysts.

The top-down synthesis and deposition of polyoxometalate-like clusters on porous carbon is reported together with the high electrocatalytic oxygen reduction reactivity of the composite.     

Universal T/B Scaling Behavior of Heavy Fermion Compounds (Brief Review)

JETP Letters - In this brief review, we address manifestations of the T/B scaling behavior of heavy-fermion (HF) compounds, where T and B are the temperature and magnetic field, respectively. Using...     

Evidence for Non-Innocence of a β-Diketonate Ligand

β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac⁻) to Cr^II spontaneously affords Cr^III and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry.     

Direct C(sp2)C(sp3) Cross‐Coupling of Diaryl Zinc Reagents with Benzylic,Primary, Secondary,and Tertiary Alkyl Halides

The direct C(sp²)? C(sp³) cross‐coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides proceeded in the absence of coordinating ethereal solvents at ambient temperature without the addition of a catalyst. The C(sp²)? C(sp³) cross‐coupling showed excellent functional‐group tolerance, and products were isolated in high yields, generally without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the construction of new C(sp²)? C(sp³) bonds.