A TEMPO-catalyzed oxidation–reduction method to probe surface and anhydrous crystalline-core domains of cellulose microfibril bundles

Cellulose - A modified TEMPO-catalyzed oxidation of the solvent-exposed glucosyl units of cellulose to uronic acids, followed by carboxyl reduction with NaBD4 to 6-deutero- and...     

A Scalable Biomimetic Synthesis of Resveratrol Dimers and Systematic Evaluation of their Antioxidant Activities

An efficient synthetic route to the resveratrol oligomers quadrangularin A and pallidol is reported. It features a scalable biomimetic oxidative dimerization that proceeds in excellent yield and with complete regioselectivity. A systematic evaluation of the natural products and their synthetic precursors as radical‐trapping antioxidants has revealed that, contrary to popular belief, this mode of action is unlikely to account for their observed biological activity.     

Solid-State NMR Spectroscopy: A Powerful Technique to Directly Study Small Gas Molecules Adsorbed in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development.     

Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

Computational and dynamic NMR investigation of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane

The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by ¹H- and ¹³C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C₂ symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a C_s transition state with a calculated relative free energy of 11.0 kcal mol⁻¹. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol⁻¹ at 298 K.     

Solvent-Free Synthesis of Nano Zirconium Phenylphosphonates with Molten Phenylphosphonic Acid

Nanosized α-zirconium phenylphosphonate particles were successfully prepared by the reaction between different zirconium sources and molten phenylphosphonic acid in the absence of solvent. The resultant nanoplates exhibit particle sizes in the range of 15 to 30 nm. The use of a topotactic anion exchange method starting from α-zirconium phosphate instead resulted in the generation of 15 to 180 nm plates, while also resulting in nanoparticles with a higher degree of crystallinity. The topotactic anion exchange of the phosphate groups by phenylphosphonate groups could be performed to completion when performed in molten phenylphosphonic acid. Characterization of both the final products as well as the individual steps in the anion exchange were performed by powder XRD, fast neutron activation analysis, TGA, FTIR spectroscopy, TEM, solid-state NMR and XPS.     

Multiple quantum well mixing and index-guided quantum well heterostructure lasers by MeV ion implantation

In recent years considerable interest has been shown in impurity-induced compositional disordering of III–V compound semiconductor devices, especially in efforts directed towards fabricating index-guided buried heterostructure lasers and other unique photonic and electronic devices. In this work we describe the study of compositional disordering induced by MeV implantation of oxygen and krypton into AlAs-GaAs superlattices and the fabrication of index-guided quantum well heterostructure lasers by MeV oxygen ion implantation.     

A graphical approach to computing Selmer groups of congruent number curves

Let E _n:y ²=x ³−n ² x denote the family of congruent number elliptic curves. Feng and Xiong (2004) equate the nontriviality of the Selmer groups associated with E _n to the presence of certain types of partitions of graphs associated with the prime factorization of n. In this paper, we extend the ideas of Feng and Xiong in order to compute the Selmer groups of E _n. 2000 Mathematics Subject Classification Primary—11G05; Secondary—14H52, 14H25, 05C90     

The enumerative geometry of surfaces and modular forms

Let be a surface, and let be a holomorphic curve in representing a primitive homology class. We count the number of curves of geometric genus with nodes passing through generic points in in the linear system for any and satisfying .

When , this coincides with the enumerative problem studied by Yau and Zaslow who obtained a conjectural generating function for the numbers. Recently, Göttsche has generalized their conjecture to arbitrary in terms of quasi-modular forms. We prove these formulas using Gromov-Witten invariants for families, a degeneration argument, and an obstruction bundle computation. Our methods also apply to blown up at 9 points where we show that the ordinary Gromov-Witten invariants of genus constrained to points are also given in terms of quasi-modular forms.     

Computing the conjugate of convex piecewise linear-quadratic bivariate functions

We present a new algorithm to compute the Legendre–Fenchel conjugate of convex piecewise linear-quadratic (PLQ) bivariate functions. The algorithm stores a function using a (primal) planar arrangement. It then computes the (dual) arrangement associated with the conjugate by looping through vertices, edges, and faces in the primal arrangement and building associated dual vertices, edges, and faces. Using optimal computational geometry data structures, the algorithm has a linear time worst-case complexity. We present the algorithm, and illustrate it with numerical examples. We proceed to build a toolbox for convex bivariate PLQ functions by implementing the addition, and scalar multiplication operations. Finally, we compose these operators to compute classical convex analysis operators such as the Moreau envelope, and the proximal average.