Some connections between frames of radical ideals and frames of <Emphasis Type="Italic">z</Emphasis>-ideals

For any semisimple f-ring A with bounded inversion, we show that the frame of radical ideals of A and the frame of z-ideals of A have isomorphic subfit coreflections. If we assume the Axiom of Choice, then the two coreflections are actually identical. If the f-ring has the property that the sum of two z-ideals is a z-ideal (as in the case of rings of continuous functions), then the epicompletion of the frame of z-ideals is shown to be a dense quotient of the epicompletion of the frame of radical ideals. Baer rings, exchange rings, and normal rings that lie in the class of semisimple f-rings with bounded inversion are shown to have characterizations in terms of frames of z-ideal which are similar to characterizations in terms of frames of radical ideals.     

Cryogenic 35 GHz pulse ENDOR probehead accommodating large sample sizes: Performance and applications

The construction and performance of a cryogenic 35 GHz pulse electron nuclear double resonance (ENDOR) probehead for large samples is presented. The resonator is based on a rectangular TE₁₀₂ cavity in which the radio frequency (rf) B₂-field is generated by a two turn saddle ENDOR coil crossing the resonator along the sample axis with minimal distance to the sample tube. An rf power efficiency factor is used to define the B₂-field strength per square-root of the transmitted rf power over the frequency range 2–180 MHz. The distributions of the microwave B₁- and E₁-field, and the rf B₂-field are investigated by electromagnetic field calculations. All dielectrics, the sample tube, and coupling elements are included in the calculations. The application range of the probehead and the advantages of using large sample sizes are demonstrated and discussed on a number of paramagnetic samples containing transition metal ions.     

Synthesis of the acylphloroglucinols rhodomyrtone and rhodomyrtosone B

In a sequential three-component coupling syncarpic acid, 3-methylbutanal and an acylated phloroglucinol were combined to the hydroxy ketone 3. Acid catalysis converted 3 directly to the natural product rhodomyrtosone B (2). The other isomer, the antibiotic rhodomyrtone (1) was obtained from 3 in a sequence of acid-catalyzed cyclization, retro Friedel–Crafts reaction, and reacylation. In preliminary assays both compounds showed potent antibiotic activity.     

2‐(4′‐Pyridyl‐N‐oxide)‐Substituted Hemithioindigos as Photoresponsive Guests for a Super Aryl‐Extended Calix[4]pyrrole Receptor

We report the synthesis of two 2‐(4′‐pyridyl‐N‐oxide)‐substituted hemithioindigos (HTIs). We probed their photoisomerization by using UV/Vis and ¹H NMR spectroscopy techniques. Light irradiation at λ=450 nm provoked the isomerization of the HTI Z isomer to the E counterpart to a large extent (≈80 % at the photostationary state). ¹H NMR titration experiments revealed the formation of thermodynamically and kinetically stable 1:1 inclusion complexes of the (Z)‐HTI isomers with a super aryl‐extended host (association constant>10⁴ m ^?1). Photoirradiation at λ=450 nm of the inclusion complexes induced the isomerization of the bound HTI N‐oxide to afford the (E)‐HTI?calix[4]pyrrole complex. We determined accurate association constant values for the 1:1 inclusion complexes of the (Z)‐ and (E)‐HTI isomers by using isothermal titration calorimetry experiments. The results showed that the stability constants of the (E)‐HTI complexes were 2.2–2.8‐fold lower than those of the (Z)‐HTI counterparts, which explains the lack of light‐induced release of the former to the bulk solution.     

Queueing and Fluid Analysis of Partial Message Discarding Policy

We consider a stream of packets that arrive at a queue with a finite buffer. A group of consecutive packets constitutes a frame. We assume that when an arriving packet finds the queue full, not only is the packet lost but also the future packets that belong to the same frame will be rejected. The first part of the paper deals with a detailed packet level queueing model; we obtain exact expressions for the stationary queue length distribution and the goodput ratio (i.e. the fraction of arriving frames that experience no losses). The second part deals with a fluid model and the fluid analysis leads to simple closed form expressions for the stationary workload process and the fluid goodput ratio.     

Copolymers of ethylene and sulfonated norbornene for proton exchange membranes

Terpolymers of ethylene, norbornene, and 5‐exo norbornene methyl alcohol are prepared using Pd phosphine sulfonates as catalysts. The pendant hydroxyl groups are then transformed into thioacetate groups. Films cast from the resulting polymers are then oxidized by hydrogen peroxide. This green oxidation method is found to quantitatively transform thioacetate groups into sulfonic acids, leading to the formation of sulfonated hydrocarbon ionomers. These ionomers are thermally stable, exhibit increasing conductivity up to 110 °C, and have a low water uptake, indicating that these materials are potentially interesting candidates for the preparation of fuel cell membranes. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2669–2676     

Synthesis of double perovskite and quadruple perovskite nanocrystals through post-synthetic transformation reactions

Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of Cs₃BiX₆ (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition–structure–property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.

Lead-free perovskite nanocrystals are synthesized by post-synthetic transformation reactions. The post-synthetic transformations show the structural flexibility of zero-dimensional perovskite nanocrystal materials.     

A Certified Reference Material for HPLC

A column and test samples have been produced as a Certified Reference Material (CRM) for use in HPLC. A round robin certification procedure has demonstrated that the retention and relative retention properties of the column, measured as the values of shape selectivity, hydrophobicity and ion-exchange activity at pH 7.0, under closely specified separation conditions, are reproducible irrespective of the instrument and laboratory. Concurrence with the CRM values can be used to confirm that an HPLC system is compliant with these specifications, in particular the mobile phase composition and column temperature. This will enable different laboratories to determine that they are operating under equivalent separation conditions, which is a necessary requirement for the efficient interlaboratory transferability of methods.     

Radical stabilizing effects : A comparison of transition state effects (rates of azoalkane decompositions) with calculated (ab initio) pi spin densities

Rate studies on five azoalkanes (4a-e) have been studied to assess important radical stabilizing effects. MO calculations of spin densities for three radicals with pi systems are correlated with kinetic rates of radical formation.     

A microcomputer program for estimation of copolymerization reactivity ratios

A user-friendly program has been developed to estimate copolymerization reactivity ratios based on a nonlinear minimization algorithm. The use of an optimal experimental design for copolymerization when the Mayo–Lewis model applies is presented. The applicability of the program is demonstrated using actual and simulated experimental data.