Encapsulation of conventional and unconventional water dimers by water-binding foldamers

Water-binding foldamers have been rarely studied. By orienting both H-bond donors and acceptors toward their interior, two pyridine-derived crescent-shaped folding oligoamides were found to be capable of trapping both conventional and unconventional water dimer clusters in their cavity (～2.5 ? radius). In the unconventional water dimer cluster, the two water molecules stay in contact via an unusual H-H interaction (2.25 ?) rather than the typical H-bond.     

Does Hydrogen‐Bonding Donation to Manganese(IV)–Oxo and Iron(IV)–Oxo Oxidants Affect the Oxygen‐Atom Transfer Ability? A Computational Study

Iron(IV)–oxo intermediates are involved in oxidations catalyzed by heme and nonheme iron enzymes, including the cytochromes P450. At the distal site of the heme in P450 Compound I (Fe^IV–oxo bound to porphyrin radical), the oxo group is involved in several hydrogen‐bonding interactions with the protein, but their role in catalysis is currently unknown. In this work, we investigate the effects of hydrogen bonding on the reactivity of high‐valent metal–oxo moiety in a nonheme iron biomimetic model complex with trigonal bipyramidal symmetry that has three hydrogen‐bond donors directed toward a metal(IV)–oxo group. We show these interactions lower the oxidative power of the oxidant in reactions with dehydroanthracene and cyclohexadiene dramatically as they decrease the strength of the O? H bond (BDE_OH) in the resulting metal(III)–hydroxo complex. Furthermore, the distal hydrogen‐bonding effects cause stereochemical repulsions with the approaching substrate and force a sideways attack rather than a more favorable attack from the top. The calculations, therefore, give important new insights into distal hydrogen bonding, and show that in biomimetic, and, by extension, enzymatic systems, the hydrogen bond may be important for proton‐relay mechanisms involved in the formation of the metal–oxo intermediates, but the enzyme pays the price for this by reduced hydrogen atom abstraction ability of the intermediate. Indeed, in nonheme iron enzymes, where no proton relay takes place, there generally is no donating hydrogen bond to the iron(IV)–oxo moiety.     

Characterizations and Electric Conductivities of Phosphorous Oxychloride-Treated Polymers Containing Methyl Vinyl Ketone

Abstract

Studies have been made on the characterizations and conductivities of poly(methyl vinyl ketone) (PMVK) and its copolymer with methyl methacrylate (poly(MVK-co-MMA)) after being reacted with phosphorus oxychloride (POCl₃). The POCl₃?treated polymers containing methyl vinyl ketone (MVK) were characterized by IR and UV spectroscopies to prove the structure of conjugated double bonds. The conductivities of all the MVK-containing polymers treated with POCl₃ were very low, ca. 10^?17 S/cm, in a vacuum regardless of the treatment time. The conductivities of the polymers when doped with iodine are in the range of the order of 10^?4 to 10^?6 S/cm. It was found that the conductivity of the POCl₃?treated copolymer is slightly lower than that of PMVK.     

Reverse Mathematics and parameter-free Transfer

Recently, conservative extensions of Peano and Heyting arithmetic in the spirit of Nelson's axiomatic approach to Nonstandard Analysis, have been proposed. In this paper, we study the Transfer axiom of Nonstandard Analysis restricted to formulas without parameters. Based on this axiom, we formulate a base theory for the Reverse Mathematics of Nonstandard Analysis and prove some natural reversals, and show that most of these equivalences do not hold in the absence of parameter-free Transfer.     

On transformations of constant depth propositional proofs

This paper studies the complexity of constant depth propositional proofs in the cedent and sequent calculus. We discuss the relationships between the size of tree-like proofs, the size of dag-like proofs, and the heights of proofs. The main result is to correct a proof construction in an earlier paper about transformations from proofs with polylogarithmic height and constantly many formulas per cedent.     

Asymmetric electrocyclic reactions

This critical review offers an overview of asymmetric electrocyclic processes, where diastereo- or enantioselectivity is a consequence of the influence of a chiral component (be it substrate or catalyst) on the electrocyclic bond-forming process (195 references).     

A new angle on pluronic additives: advancing droplets and understanding in digital microfluidics

Biofouling in microfluidic devices limits the type of samples which can be handled and the duration for which samples can be manipulated. Despite the cost of disposing fouled devices, relatively few strategies have been developed to tackle this problem. Here, we have analyzed a series of eight amphiphilic droplet additives, Pluronic coblock polymers of poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO), as a solution to biofouling in digital microfluidics using serum-containing cell culture media as a model fluid. Our analysis shows that species with longer PPO chains are superior for enabling droplet motion and reducing biofouling. Two of the tested species, L92 and P105, were found to lengthen device lifetimes by 2-3 times relative to additives used previously when used at optimal concentrations. Pluronics with low PEO content such as L92 were found to be cytotoxic to an immortalized mammalian cell line, and therefore we recommend that Pluronic additives with greater or equal to 50% PEO composition, such as P105, be used for digital microfluidic applications involving cells. Finally, contact angle measurements were used to probe the interaction between Pluronic-containing droplets and device surfaces. Strong correlations were found between various types of contact angle measurements and the capacity of additives to reduce biofouling, which suggests that contact angle measurements may be useful as a tool for rapidly screening new candidates for the potential to reduce biofouling. We propose that this study will be useful for scientists and engineers who are developing digital microfluidic platforms for a wide range of applications involving protein-containing solutions, and in particular, for applications involving cells.     

Magnetic ordering in the frustrated system FeSc2S4

The sample of FeSc₂S₄ was prepared by solid reaction method. The crystallographic structure and the magnetic properties of the fabricated compound were investigated by X-ray, and superconducting quantum interference device (SQUID) magnetometer and Mössbauer spectroscopy. The polycrystalline FeSc₂S₄ confirmed the normal cubic spinel structure (space group Fd3m). The lattice constants a₀ and anion parameter u are 10.519 Å and 0.255, respectively. The Mössbauer spectroscopy has been studied for the FeSc₂S₄ at various temperatures, ranging from 4.2 K to room temperature. The spectra consist of two doublets at 4.2 K while a single line at room temperature. It is noticeable that the Mössbauer spectra of two doublet patterns with large electric quadrupole splitting (ΔE_Q) remain over the Néel temperature. Those are interpreted as a result of large electric quadrupole interaction compared to magnetic dipole interaction. The magnetic susceptibility measurements were performed with a SQUID magnetometer for temperatures 2<T<320 K, in external fields up to 5 kOe. Magnetic behavior shows antiferromagnetic behavior and the magnetic superexchange interactions between the Fe ions are weakly antiferromagnetic. The paramagnetic susceptibilities follow Curie–Weiss (CW) law with CW temperature Θ_CW=−100 K, and frustration parameter f=−Θ_CW/T_N is of the order of 1000. We conclude that two sublattices are coupled antiferromagnetically, leading to strong frustration effects.     

Structure and electronic properties of native and defected gallium nitride nanotubes

Structure and electronic properties of GaN nanotubes (GaNNTs) are investigated by using ab initio density functional theory. By full optimization, the optimized structures (bond-lengths and angles between them) of zigzag GaNNTs (n,0) and armchair GaNNTs (n,n) (4<n<11) are calculated. The difference between nitrogen ring diameter and gallium ring diameter (buckling distance) and semiconducting energy gap in term of diameter for zigzag and armchair GaNNTs have also been calculated. We found that buckling distance decreases by increasing nanotube diameter. Furthermore, we have investigated the effects of nitrogen and gallium vacancies on structure and electronic properties of zigzag GaNNT (5,0) using spin dependent density functional theory. By calculating the formation energy, we found that N vacancy in GaNNT (5,0) is more favorable than Ga vacancy. The nitrogen vacancy in zigzag GaNNT induces a 1.0μB magnetization and makes a polarized structure. We have shown that in polarized GaNNT a flat band near the Fermi energy splits to occupied spin up and unoccupied spin down levels.