σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

In this work, the largest heterometallic supertetrahedral clusters, [Zn₆Ge₁₆]⁴⁻ and [Cd₆Ge₁₆]⁴⁻, were directly self-assembled through highly-charged [Ge₄]⁴⁻ units and transition metal cations, in which 3-center–2-electron σ bonding in Ge₂Zn or Ge₂Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time-dependent HRESI-MS spectra show that the larger clusters grow from smaller components with a single [Ge₄]⁴⁻ and ZnMes₂ units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M₆Ge₁₆]⁴⁻ (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.     

Stability,electronic, and optical properties of two-dimensional phosphoborane

The structure and properties of two-dimensional phosphoborane sheets were computationally investigated using Density Functional Theory calculations. The calculated phonon spectrum and band structure point to dynamic stability and allowed characterization of the predicted two-dimensional material as a direct-gap semiconductor with a band gap of ~1.5 eV. The calculation of the optical properties showed that the two-dimensional material has a relatively small absorptivity coefficient. The parameters of the mechanical properties characterize the two-dimensional phosphoborane as a relatively soft material, similar to the monolayer of MoS₂. Assessment of thermal stability by the method of molecular dynamics indicates sufficient stability of the predicted material, which makes it possible to observe it experimentally.     

Electrochemically driven C–N bond formation from CO2 and ammonia at the triple-phase boundary

Electrosynthetic techniques are gaining prominence across the fields of chemistry, engineering and energy science. However, most works within the direction of synthetic heterogeneous electrocatalysis focus on water electrolysis and CO₂ reduction. In this work, we moved to expand the scope of small molecule electrosynthesis by developing a synthetic scheme which couples CO₂ and NH₃ at a gas–liquid–solid boundary to produce species with C–N bonds. Specifically, by bringing in CO₂ from the gas phase and NH₃ from the liquid phase together over solid copper catalysts, we have succeeded in forming formamide and acetamide products for the first time from these reactants. In a subsequent complementary step, we have combined electrochemical analysis and a newly developed operando spectroelectrochemical method, capable of probing the aforementioned gas–liquid–solid boundary, to extract an initial level of mechanistic analysis regarding the reaction pathways of these reactions and the current system''s limitations. We believe that the development and understanding of this set of reaction pathways will play significant role in expanding the community''s understanding of on-surface electrosynthetic reactions as well as push this set of inherently sustainable technologies towards widespread applicability.

Electrocatalytic formation of C–N bonds was achieved through the electrolysis of CO₂ and NH₃ over Cu catalysts. A combined analytical and spectroscopic approach gave insights into the reaction mechanism leading to formamide and acetamide products.     

A series of three-dimensional coordination polymers with general formula [{Ln(H2O)n}{Re6Te8(CN)6}] · xH2O (Ln = Eu,Gd, Tb,Dy, Ho,Er, Tm,Yb; n = 3, 4, x = 0, 2.5)

A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re₆Te₈(CN)₆]³⁻ was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H₂O)₄}{Re₆Te₈(CN)₆}] · 2.5H₂O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H₂O)₃}{Re₆Te₈(CN)₆}] · 2.5H₂O (2) and [{Yb(H₂O)₄}{Re₆Te₈(CN)₆}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μ_B for compound 2 and 10.79 μ_B for compound 5 with weak antiferromagnetic ordering appeared at low temperatures.     

Positron spectroscopy analysis in metallocene propylene/1‐octadecene copolymers: Parameters dependence on monoclinic and mesomorphic polymorphs

Copolymers of propylene and 1‐octadecene synthesized by a metallocene catalyst were characterized by PALS, WAXD, DSC, and density measurements. The change in the sizes and the number density of free‐volume holes as a function of the 1‐octadecene content were compared to the master laws published for copolymers of propylene with α‐olefins of shorter lengths. It was found that the samples were separated into two groups. The first set of samples obeyed the master laws while the second group deviated. This behavior was explained by the difference in the copolymer structure. The WAXD analysis confirmed the separation as well. The deviation was explained as due to the mesomorphic crystalline structure of the second group of samples, in contrast to the monoclinic one for the first group, which was a result of the relatively fast cooling from the molten state and from the high comonomer molar content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1994–2002, 2010     

Vibrations of a continuous web on elastic supports

We consider an infinite, homogenous linearly elastic beam resting on a system of linearly elastic supports, as an idealized model for a paper web in the middle of a cylinder-based dryer section. We obtain closed-form analytical expressions for the eigenfrequencies and the eigenmodes. The frequencies increase as the support rigidity is increased. Each frequency is bounded from above by the solution with absolutely rigid supports, and from below by the solution in the limit of vanishing support rigidity. Thus in a real system, the natural frequencies will be lower than predicted by commonly used models with rigid supports.     

Ionic liquid matrices for MALDI mass spectrometry of lignin

Analytical and Bioanalytical Chemistry - The use of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry for the study of lignin is still extremely limited due to its low...     

Quantifying induced electric field strengths during gene transfer to the intact rat vasculature

The application of appropriate electric fields to cells and tissues, termed electroporation, can result in efficient and safe gene transfer. We have shown previously that this approach results in high level gene transfer to and expression in the vasculature of living animals. This paper presents the results of an electric field distribution study of a rat mesenteric vasculature model using the Finite-Element Time-Domain (FETD) technique. A novelty of this work is the use of Debye dispersive dielectric parameters, as the electrical response of biological tissues is inherently frequency-dependent. The results compare fairly well with experimental findings.