2,6‐Bis[bis(2‐pyridiniomethyl)aminomethyl]‐4‐tert‐butylphenol dichloride diperchlorate hydrate

The title compound, C₃₆H₄₄N₆O⁴⁺·2Cl^?·2ClO₄^?·0.132H₂O, is shown to be protonated at all the pyridine N atoms; the two chloride ions are hydrogen bonded to three pyridine N atoms and to the phenolic O atom of the same cation [Cl?N = 3.045 (2)–3.131 (2) Å and Cl?O = 2.938 (2) Å], and the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N?O = 2.861 (2) Å]. The mean value of the C—N—C angle of the protonated pyridine rings is 123.4 (1)°, which is significantly larger than that found for unprotonated pyridine rings.     

Association of 25-hydroxyvitamin D3)levels in adult New Zealanders with ethnicity, skin color and self-reported skin sensitivity to sun exposure

The study aim was to determine the contribution of ethnicity, objectively measured skin color and skin reaction-to-sun exposure to variations in 25-hydroxyvitamin D(3) [25(OH)D(3) ]. A multiethnic sample (European, Maori, Pacific and Asian) of 503 adult volunteers aged 18-85 years, recruited from Auckland and Dunedin in New Zealand, answered a questionnaire on sun exposure and self-defined ethnicity. Skin color was measured using a spectrophotometer and the Individual Typology Angle (ITA) calculated. A blood sample was collected 4 weeks later to measure 25(OH)D(3). 25(OH)D(3) was associated with ethnicity, but not self-reported skin reaction-to-sun exposure. Amongst the ethnic groups, Asians had the lowest mean 25(OH)D level (37.0 nmol L(-1)) and Europeans with lighter colored skin had the highest (57.9 nmol L(-1)). An association also was seen between 25(OH)D(3) and skin color, with an increase of 2-3 nmol L(-1) per 10° increase in ITA value, indicating higher 25(OH)D(3) with lighter skin color; but much of this association disappeared after adjusting for ethnicity. In contrast, ethnicity remained associated with 25(OH)D(3) after adjusting for ITA skin color and skin reaction-to-sun exposure. These results indicate that self-defined ethnicity was a major determinant of variations in serum 25(OH)D(3), while objective measures of skin color explained relatively little additional variation.     

Initialisation in RAFT-mediated polymerisation of methyl acrylate

Inhibition in Reversible Addition-Fragmentation chain Transfer (RAFT)-mediated polymerisations is currently a controversial issue; here we provide evidence that the slow "propagation" of the initiating and leaving group radicals during the early part (the period of consumption of the initial RAFT agent) of methyl acrylate RAFT-mediated polymerisation has characteristics similar to inhibition.     

Plasma‐Activated Substrate with a Tropoelastin Anchor for the Maintenance and Delivery of Multipotent Adult Progenitor Cells

Conventional wound therapy utilizes wound coverage to prevent infection, trauma, and fluid and thermal loss. However, this approach is often inadequate for large and/or chronic wounds, which require active intervention via therapeutic cells to promote healing. To address this need, a patch which delivers multipotent adult progenitor cells (MAPCs) is developed. Medical‐grade polyurethane (PU) films are modified using plasma immersion ion implantation (PIII), which creates a radical‐rich layer capable of rapidly and covalently attaching biomolecules. It is demonstrated that a short treatment duration of 400 s maximizes surface activation and wettability, minimizes reduction in gas permeability, and preserves the hydrolytic resistance of the PU film. The reactivity of PIII‐treated PU is utilized to immobilize the extracellular matrix protein tropoelastin in a functional conformation that stably withstands medical‐grade ethylene oxide sterilization. The PIII‐treated tropoelastin‐functionalized patch significantly promotes MAPC adhesion and proliferation over standard PU, while fully maintaining cell phenotype. Topical application of the MAPC‐seeded patch transfers cells to a human skin model, while undelivered MAPCs repopulate the patch surface for subsequent cell transfer. The potential of this new wound patch as a reservoir for the sustained delivery of therapeutic MAPCs and cell‐secreted factors for large and/or non‐healing wounds is indicated in the findings.     

Synthesis and characterization of fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties

The new monomer 2,2-bis[4-(4-{4-fluorobenzoyl}-1-naphthoxy)phenyl]hexafluoropropane ( 2 ) was synthesized in a two-step reaction sequence. 2,2-his[4-(1-naphthoxy)phenyl]-hexafluoropropane ( 1 ) was prepared using the Ullmann ether synthesis reaction of 4,4-(hex-afluoroisopropylidiene)diphenol with 1-bromonaphthalene. Friedel-Crafts acylation of 1 with 4-fluorobenzoyl chloride in methylene chloride containing dimethylsulfone selectively afforded 2 in 82% yield. The polycondensation of 2 with various bisphenols in DMAc in the presence of an excess of potassium carbonate as a condensation reagent was carried out at 165°C to quantitatively afford the corresponding fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties. Thermal analysis of the polymers showed them to have T_gs ranging from 194 to 230°C and to be thermally stable in air up with initial weight losses at about 500°C. In addition, these novel polymers exhibited excellent solubility in organic solvents including NMP, DMAc, and chloroform. © 1997 John Wiley & Sons, Inc.     

Conformational analysis: crystallographic,NMR, and molecular mechanics studies of flexible sulfonic esters

Two novel X-ray structures of the sulfonic ester derivatives 2-(6-iodo-1,3-benzodioxol-5-yl)ethyl 4-nitrobenzenesulfonate, 3, and 2-(6-iodo-1,3-benzodioxol-5-yl)ethyl 4-methylbenzenesulfonate, 4, have been obtained in a study aimed at analyzing the structures and conformations of sulfonic ester derivatives that are routinely used in alkaloid syntheses. The crystal structure of 4 is highly unusual, containing four independent molecules that belong to two distinct conformational types: (1) a hairpin conformation (stabilized mainly by intramolecular pi-stacking) and (2) a stepped conformation (stabilized mainly by intermolecular pi-stacking). Compound 3, on the other hand, crystallizes exclusively as the hairpin conformer. New MM+ force field parameters for sulfonic esters have been developed using the X-ray data, empirical rules, and DFT calculations to estimate the bond dipole parameters. Grid searches of conformational space for 3 and 4 using MM methods show that there are several gas-phase conformations within 5 kcal/mol of the global minimum and that the lowest energy conformations (by approximately 4.6 kcal/mol) are of the hairpin type. Analysis of the MM conformational energies suggests that the dominant intramolecular interaction stabilizing the hairpin conformations of 3 and 4 is van der Waals attraction. Moreover, the lattice energies for packing the hairpin conformations of 3 and 4 are approximately 4 kcal/mol more favorable than for the stepped conformations. Various intermolecular interactions contribute to the complexity of the observed crystal structures of 3 and 4, including electrostatic attraction between O and I atoms in neighboring molecules. Langevin dynamics (LD) simulations at several temperatures (6.0 ns, friction coefficient = 2.5 ps(-1)) indicate that the conformational exchange rates are approximately 10(10)-10(11) s(-1) over the temperature range 213-400 K, accounting for the temperature-independent (1)H NMR spectra of 3 and 4.     

Para primal varieties: A study of finite axiomatizability and definable principal congruences in locally finite varieties

We introduce new sufficient conditions for a finite algebraU to possess a finite basis of identities. The conditions are that the variety generated byU possess essentially only finitely many subdirectly irreducible algebras, and have definable principal congruences. Both conditions are satisfied if this variety is directly representable by a finite set of finite algebras. One task of the paper is to show that virtually no lattice varieties possess definable principal congruences. However, the main purpose of the paper is to apply the new criterion in proving that every para primal variety (congruence permutable variety generated by finitely many para primal algebras) is finitely axiomatizable. The paper also contains a completely new approach to the structure theory of para primal varieties which complements and extends somewhat the recent work of Clark and Krauss.     

Phase-constrained parallel MR image reconstruction

A generalized method for phase-constrained parallel MR image reconstruction is presented that combines and extends the concepts of partial-Fourier reconstruction and parallel imaging. It provides a framework for reconstructing images employing either or both techniques and for comparing image quality achieved by varying k-space sampling schemes. The method can be used as a parallel image reconstruction with a partial-Fourier reconstruction built in. It can also be used with trajectories not readily handled by straightforward combinations of partial-Fourier and SENSE-like parallel reconstructions, including variable-density, and non-Cartesian trajectories. The phase constraint specifies a better-conditioned inverse problem compared to unconstrained parallel MR reconstruction alone. This phase-constrained parallel MRI reconstruction offers a one-step alternative to the standard combination of homodyne and SENSE reconstructions with the added benefit of flexibility of sampling trajectory. The theory of the phase-constrained approach is outlined, and its calibration requirements and limitations are discussed. Simulations, phantom experiments, and in vivo experiments are presented.