Synthesis and structure of an ether-bridged double ladder compound: potential in host - guest chemistry

The synthesis of the first example of an organotin double ladder (6) containing a functional group within the spacer is reported. In the solid state, compound 6 shows an interlaminar cavity whose size and shape suggest the possibility of host–guest chemistry. ¹¹⁹Sn-NMR and ESMS show that compound 6 undergoes extensive dissociation in solution. ESMS of compound 6 to which have been added Li⁺, Na⁺, Mg²⁺ or Cu²⁺ show only minimal interaction.

Hypercoordinated organotin compounds containing sulfur and chlorine. Molcular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]- (R=Me, t-Bu)

The reaction of diorganotin sulfides, cyclo-(R₂SnS)_n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R₂SnCl₂, provided the tetraorganodistannathianes, (R₂ClSn)₂S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). ¹H-, ¹³C-, and ¹¹⁹Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition of equimolar amounts of [(Ph₃P)₂N]Cl to the reaction mixtures gave the chloride complexes [(Ph₃P)₂N]⁺[S(SnR₂Cl)₂Cl]⁻ (4, R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions.

Novel 10- and 20- membered tin- and silicon-containing rings: synthesis, complexation behavior and conversion into a lewis acidic polymer

Reaction of the dimethylsilylmethyl-substituted tetraorganotin derivative CH₂[CH₂Sn(Ph₂)CH₂Si(H)Me₂]₂ (1) and CH₂[CH₂Sn(Ph₂)CH₂Si(i-PrO)Me₂]₂ (3), respectively, with mercuric chloride afforded the novel silicon- and tin-containing 10- and 20-membered rings cyclo-CH₂[CH₂Sn(Cl₂)CH₂Si(Me₂)]₂O (4) and cyclo-CH₂[CH₂Sn(Cl₂)CH₂Si(Me₂)OSi(Me₂)CH₂Sn(Cl₂)CH₂]₂CH₂ (5). Both compounds 4 and 5 can be converted into the soluble Lewis acidic polymer poly-[Si(Me₂)CH₂Sn(Cl₂)(CH₂)₃Sn(Cl₂)CH₂Si(Me₂)O] (8). ¹¹⁹Sn NMR studies indicate that 4 acts as a bidentate Lewis acid toward chloride ions, exclusively forming the 1:1 complex [cyclo-CH₂[CH₂Sn(Cl₂)CH₂Si(Me₂)]₂O·Cl]-[(Ph₃P)₂N]⁺ (7). The molecular structures as determined by single-crystal X-ray diffraction analysis of 4 and 7 are reported.

Comparison of the color stability and lipid oxidative stability of fresh vacuum packaged lamb muscle containing elevated omega-3 and omega-6 fatty acid levels from dietary manipulation

A series of three experiments were conducted with second cross ([Merino×Border Leicester]×Poll Dorset) wether lambs to evaluate the effects of dietary treatments on manipulation of muscle long-chain (LC) omega-3 fatty acids (FA) on the color stability and oxidative stability of fresh and vacuum packaged lamb. At the end of 7-, 6- and 6-week experimental periods for experiments (Exp.) 1–3 respectively, lambs were slaughtered at a commercial abattoir. At 24 h post-mortem, muscle longissimus lumborum (LL) and longissimus thoracis (LT) were removed and evaluated for color and lipid oxidative stability under specified commercial storage and display condition. Of the dietary supplements used, fish meal and fish oil moderately (P<0.01) and markedly (P<0.001) increased muscle omega-3 FA content, while both protected canola seed (P<0.001) and protected sunflower meal protein significantly (P<0.02) increased muscle omega-6 FA content or ratio of omega-6/omega-3 of the longissimus muscle. In all experiments, the substantial increase (P<0.001) in muscle LC omega-3 and omega-6 FA had no consistent significant effect on color values (redness (a*), yellowness (b*) and lightness (L*)) for fresh and vacuum packaged lamb over a 6-day display period. Lipid oxidation, determined by the levels of thiobarbituric acid reactive substances (TBARS) indicated the enrichment of muscle polyunsaturated fatty acid (PUFA) levels in lambs did not produce significant differences resulting either from main treatment effects or for treatment×day×type interactions (where type was fresh and vacuum packaged). Present results demonstrated the color and lipid oxidative stability of lamb longissimus muscle during refrigerated display was not affected by enhanced levels of omega-3 and omega-6 FA due to dietary treatments.

Comparison of the color stability and lipid oxidative stability of fresh and vacuum packaged lamb muscle containing elevated omega-3 and omega-6 fatty acid levels from dietary manipulation

A series of three experiments were conducted with second cross ([Merino×Border Leicester]×Poll Dorset) wether lambs to evaluate the effects of dietary treatments on manipulation of muscle long-chain (LC) omega-3 fatty acids (FA) on the color stability and oxidative stability of fresh and vacuum packaged lamb. At the end of 7-, 6- and 6-week experimental periods for experiments (Exp.) 1–3 respectively, lambs were slaughtered at a commercial abattoir. At 24 h post-mortem, muscle longissimus lumborum (LL) and longissimus thoracis (LT) were removed and evaluated for color and lipid oxidative stability under specified commercial storage and display condition. Of the dietary supplements used, fish meal and fish oil moderately (P<0.01) and markedly (P<0.001) increased muscle omega-3 FA content, while both protected canola seed (P<0.001) and protected sunflower meal protein significantly (P<0.02) increased muscle omega-6 FA content or ratio of omega-6/omega-3 of the longissimus muscle. In all experiments, the substantial increase (P<0.001) in muscle LC omega-3 and omega-6 FA had no consistent significant effect on color values (redness (a*), yellowness (b*) and lightness (L*)) for fresh and vacuum packaged lamb over a 6-day display period. Lipid oxidation, determined by the levels of thiobarbituric acid reactive substances (TBARS) indicated the enrichment of muscle polyunsaturated fatty acid (PUFA) levels in lambs did not produce significant differences resulting either from main treatment effects or for treatment×day×type interactions (where type was fresh and vacuum packaged). Present results demonstrated the color and lipid oxidative stability of lamb longissimus muscle during refrigerated display was not affected by enhanced levels of omega-3 and omega-6 FA due to dietary treatments.

Comparison of the color stability and lipid oxidative stability fo fresh and vacuum packaged lamb muscle containing elevated omega-3 and omega-6 fatty acid levels from dietary manipulation

A series of three experiments were conducted with second cross ([Merino×Border Leicester]×Poll Dorset) wether lambs to evaluate the effects of dietary treatments on manipulation of muscle long-chain (LC) omega-3 fatty acids (FA) on the color stability and oxidative stability of fresh and vacuum packaged lamb. At the end of 7-, 6- and 6-week experimental periods for experiments (Exp.) 1–3 respectively, lambs were slaughtered at a commercial abattoir. At 24 h post-mortem, muscle longissimus lumborum (LL) and longissimus thoracis (LT) were removed and evaluated for color and lipid oxidative stability under specified commercial storage and display condition. Of the dietary supplements used, fish meal and fish oil moderately (P<0.01) and markedly (P<0.001) increased muscle omega-3 FA content, while both protected canola seed (P<0.001) and protected sunflower meal protein significantly (P<0.02) increased muscle omega-6 FA content or ratio of omega-6/omega-3 of the longissimus muscle. In all experiments, the substantial increase (P<0.001) in muscle LC omega-3 and omega-6 FA had no consistent significant effect on color values (redness (a*), yellowness (b*) and lightness (L*)) for fresh and vacuum packaged lamb over a 6-day display period. Lipid oxidation, determined by the levels of thiobarbituric acid reactive substances (TBARS) indicated the enrichment of muscle polyunsaturated fatty acid (PUFA) levels in lambs did not produce significant differences resulting either from main treatment effects or for treatment×day×type interactions (where type was fresh and vacuum packaged). Present results demonstrated the color and lipid oxidative stability of lamb longissimus muscle during refrigerated display was not affected by enhanced levels of omega-3 and omega-6 FA due to dietary treatments.

Self-assembly and film stability of a micelle of a single-chain quaternary ammonium amphiphile containing azobenzene on mica

The self-assembling behavior of a single-chain quaternary ammonium amphiphile bearing azobenzene (C₁₂AzoC₆N⁺) on freshly cleaved mica sheet has been investigated by atomic force microscopy (AFM) method. Confocal microscopic Raman spectra confirm the adsorption of the self-assembled monolayer structure. Ex-situ AFM reveals that C₁₂AzoC₆N⁺ forms branch-like stripes indicating the fusion and reorganization of the micelles during drying in air as the in-situ AFM has revealed that surfactant forms spherical micelles on the mica surface. The nano-sized surface structure is strongly dependent on the change of molecular structure, which resulted from photo-induced isomerization. The nano-sized stripe is quite stable even being annealed at 90 °C for 4 h.

Assembly of 3-D network structures containing oxydiacetate and CeIII or CeIV

Reaction of CeCl₃·7H₂O with Na₂(oda) (oda = O(CH₂CO₂)₂²— oxydiacetate) in a 2:3 ratio gives the neutral cerium(III) complex [Ce₂(oda)₃(H₂O)₃]·9H₂O (1). Treatment of a 1:3 mixture of CeCl₃·7H₂O and H₂oda in water with 4 molar equivalents of NaOH also gives 1 but, with a larger excess of NaOH, the tri-sodium salt Na₃[Ce(oda)₃]·9H₂O (2) is isolated. Formation of a tri-ammonium analogue of 2 can be achieved by neutralisation of an aqueous solution of CeCl₃·7H₂O and H₂(oda) in a 1:3 ratio by NH₄OH, giving (NH₄)₃[Ce(oda)₃]·7H₂O (3). Use of the cerium(IV) reagent (NH₄)₂[Ce(NO₃)₆] with Na₂(oda) results in reduction to cerium(III) under ambient conditions and isolation of 1. However, in the absence of light this reaction yields crystals of the novel cerium(IV) heterobimetallic [Ce(oda)₃Na₄(NO₃)₂] (4). Each of these complexes exhibit a 3-D network structure having a common nine-coordinate [Ce(oda)₃]ⁿ— (n = 2 or 3) subunit, irrespective of the oxidation state of cerium. In 1, six [Ce(oda)₃]³— anions are connected, through bridging bidentate carboxylates, to a second Ce³⁺ site further coordinated by three water molecules. In contrast, the ammonium salt 2, displays isolated [Ce(oda)₃]³— anions, devoid of further carboxylate bonding, but enmeshed within a network of hydrogen-bonded NH₄⁺ cations and water molecules. The remarkable structure of 4 consists of infinite 2-D sheets of [Na₂(NO₃)]+ pillared by [Ce(oda)₃]^2— units, the connectivity arising by multidentate nitrate and carboxylate bridging.

Effect of an arginine-containing nutritional supplement on pressure ulcer healing in community spinal patients

Objective: To determine whether or not the use of an arginine-containing nutritional supplement could result in signifi cantly shorter pressure ulcer (PU) healing times in people with spinal cord injuries living in the community, compared with a comparative historical control group. Method: Eighteen spinal-cord-injured patients (all part of a hospital spinal outreach service) received 9g of a commercial powdered arginine supplement per day until full PU healing occurred. Healing rates were compared against 17 historical control patients (as assessed by medical history audit). 
Results: Baseline characteristics (age, gender, injury level and time) were similar between groups. Mean ulcer healing times were 10.5 ± 1.3 weeks versus 21 ± 3.7 weeks (p<0.05) in the intervention and control groups respectively. Comparison of healing rates in the intervention group against expected healing rates derived from the medical literature showed that intervention patients had a signifi cantly shorter mean healing time (category 2 PU: 5.5±1.3 weeks versus 13.4 weeks; category 3 PU: 12.5 ± 1.9 weeks versus 18.2 weeks; category 4 PU: 14.4 ± 4.8 weeks versus 22.1 weeks). A diagnosis of diabetes did not significantly alter healing rates in either group. Conclusion: Results from this observational study show a promising benefit of arginine supplementation on PU healing for individuals with spinal cord injury living in the community.

Immunologic significance of respirable atmospheric starch granules containing major birch allergen Bet v 1

Background: Birch-pollen allergens are an important cause of early spring hay fever and allergic asthma. Recently, we reported a mechanism for the release of respirable allergenic particles from birch pollen containing the major allergen Bet v 1. In this study, we aimed to assess the immunologic significance of the released Bet v 1-containing starch granules in the environment.

Methods: A two-site monoclonal antibody-based assay (ELISA) was employed to quantitate Bet v 1 in high-volume air sampler filter extracts, and immunogold-labelling was used on sections of these extracts to localize Bet v 1. Immunoblot analyses were performed with pooled sera from patients sensitive to birch pollen.

Results: Atmospheric starch granules contained Bet v 1, and the concentration increased upon light rainfall. Sera from patients allergic to birch allergens recognized extracts from isolated starch granules.

Conclusions: The clinical implications of these findings are that starch granules released from birch pollen are potentially able to trigger allergic asthmatic reactions to Bet v 1, since the allergen occurs in respirable particles. Thus, clinicians can advise asthma patients to remain indoors on days of light rainfall during the birch-pollen season to avoid high levels of allergen exposure.