A comparison of the aroma volatiles and fatty acid compositions of grilled beef muscle from Aberdeen Angus and Holstein-Friesian steers fed diets based on silage or concentrates

This paper compares the volatile compound and fatty acid compositions of grilled beef from Aberdeen Angus and Holstein-Friesian steers slaughtered at 14 months, each breed fed from 6 months on either cereal-based concentrates or grass silage. Linoleic acid levels were higher in the muscle of concentrates-fed animals, which in the cooked meat resulted in increased levels of several compounds formed from linoleic acid decomposition. Levels of alpha-linolenic acid, and hence some volatile compounds derived from this fatty acid, were higher in the meat from the silage-fed steers. 1-Octen-3-ol, hexanal, 2-pentylfuran, trimethylamine, cis- and trans-2-octene and 4,5-dimethyl-2-pentyl-3-oxazoline were over 3 times higher in the steaks from the concentrates-fed steers, while grass-derived 1-phytene was present at much higher levels in the beef from the silage-fed steers. Only slight effects of breed were observed. (C) 2004 Elsevier Ltd. All rights reserved.

Carbohydrate-based micelle clusters which enhance hydrophobic drug bioavailability by up to 1 order of magnitude

Amphiphilic chitosan-based polymers (M-w < 20 kDa) self-assemble in aqueous media at low micromolar concentrations to give previously unknown micellar clusters of 100-300 nm in size. Micellar clusters comprise smaller 10-30 nm aggregates, and the nanopolarity/drug incorporation efficiency of their hydrophobic domains can be tailored by varying the degree of lipidic derivatization and molecular weight of the carbohydrate. The extent of drug incorporation by these novel micellar clusters is 1 order of magnitude higher than is seen with triblock copolymers, with molar polymer/drug ratios of 1:48 to 1:67. On intravenous injection, the pharmacodynamic activity of a carbohydrate propofol formulation is increased by 1 order of magnitude when compared to a commercial emulsion formulation, and on topical ocular application of a carbohydrate prednisolone formulation, initial drug aqueous humor levels are similar to those found with a 10-fold dose of prednisolone suspension.

Synthesis and biological in vitro evaluation of novel PEG-psoralen conjugates

Psoralens are well-known photosensitizers, and 8- methoxypsoralen and 4,5',8-trimethylpsoralen are widely used in photomedicine as "psoralens plus UVA therapy" (PUVA), in photopheresis, and in sterilization of blood preparations. In an attempt to improve the therapeutic efficiency of PUVA therapy and photopheresis, four poly(ethylene glycol) (PEG)-psoralen conjugates were synthesized to promote tumor targeting by the enhanced permeability and retention (EPR) effect. Peptide linkers were used to exploit specific enzymatic cleavage by lysosomal proteases. A new psoralen, 4-hydroxymethyl-4', 8-dimethylpsoralen (6), suitable for polymer conjugation was synthesized. The hydroxy group allowed exploring different strategies for PEG conjugation, and linkages with different stability such ester or urethanes were obtained. PEG (5 kDa) was covalently conjugated to the new psoralen derivative using four different linkages, namely, (i) direct ester bond (7), (ii) ester linkage with a peptide spacer (8), (iii) a carbamic linker (9), and (iv) a carbamic linker with a peptide spacer (12). The stability of these new conjugates was assessed at different pHs, in plasma and following incubation with cathepsin B. Conjugates 7 and 8 were rapidly hydrolyzed in plasma, while 9 was stable in buffer and in the presence of cathepsin B. As expected, only the conjugates containing the peptide linker released the drug in presence of cathepsin B. In vitro evaluation of the cytotoxic activity in the presence and absence of light was carried out in two cell lines (MCF-7 and A375 cells). Conjugates 7 and 8 displayed a similar activity to the free drug (probably due to the low stability of the ester linkage). Interestingly, the conjugates containing the carbamate linkage (9 and 12) were completely inactive in the dark (IC50 > 100 mu M in both cell lines). However, antiproliferative activity become apparent after UV irradiation. Conjugate 12 appears to be the most promising for future in vivo evaluation, since it was relatively stable in plasma, which should allow tumor targeting and drug release to occur by cathepsin B-mediated hydrolysis.

Melt brushes of diblock copolymer

Using self-consistent field theory (SCFT), we investigate the morphologies formed by a melt brush of AB diblock copolymers grafted to a flat substrate by their B ends. In addition to a laterally uniform morphology, SCFT predicts three ordered morphologies exhibiting different periodic patterns at the air surface: a hexagonal array of A-rich dots, an alternating sequence of A- and B-rich stripes, and a hexagonal pattern of B-rich dots. When the phase diagram of the tethered film is plotted as a function of A/B incompatibility, $\chi N$, and diblock composition, $f$, it resembles the bulk phase diagram with the periodic phases converging to a mean-field critical point at weak segregation. The periodic-phase region in the phase diagram shrinks with increasing grafting density and expands when the air surface acquires an affinity for the grafted B blocks.

Polymer − surfactant vesicular complexes in aqueous medium

The introduction of ionic single-tailed surfactants to aqueous solutions of EO18BO10 [EO = poly(ethylene oxide), BO = poly(1,2-butylene oxide), subscripts denote the number of repeating units] leads to the formation of vesicles, as probed by laser scanning confocal microscopy. Dynamic light scattering showed that the dimensions of these aggregates at early stages of development do not depend on the sign of the surfactant head group charge. Small-angle X-ray scattering (SAXS) analysis indicated the coexistence of smaller micelles of different sizes and varying polymer content in solution. In strong contrast to the dramatic increase of size of dispersed particles induced by surfactants in dilute solution, the d-spacing of corresponding mesophases reduces monotonically upon increasing surfactant loading. This effect points to the suppression of vesicles as a consequence of increasing ionic strength in concentrated solutions. Maximum enhancements of storage modulus and thermal stability of hybrid gels take place at different compositions, indicating a delicate balance between the number and size of polymer-poor aggregates (population increases with surfactant loading) and the number and size of polymer−surfactant complexes (number and size decrease in high surfactant concentrations).

Developments in block copolymer science and technology

Focuses on recent advances in research on block copolymers, covering chemistry (synthesis), physics (phase behaviors, rheology, modeling), and applications (melts and solutions). Written by a team of internationally respected scientists from industry and academia, this text compiles and reviews the expanse of research that has taken place over the last five years into one accessible resource. Ian Hamley is the world-leading scientist in the field of block copolymer research Presents the recent advances in the area, covering chemistry, physics and applications. Provides a broad coverage from synthesis to fundamental physics through to applications Examines the potential of block copolymers in nanotechnology as self-assembling soft materials

Morphologies of block copolymer melts

Morphology formation by block copolymers in the melt is reviewed, considering both theoretical and experimental aspects. Comprehensive tables provide information on morphology identification for many block copolymer systems. A particular focus is on recent structural studies on ABC triblocks and rod–coil copolymers.

Sterically controlled recognition of macromolecular sequence information by molecular tweezers

Sequence-specific binding is demonstrated between pyrene-based tweezer molecules and soluble, high molar mass copolyimides. The binding involves complementary pi - pi stacking interactions, polymer chain-folding, and hydrogen bonding and is extremely sensitive to the steric environment around the pyromellitimide binding-site. A detailed picture of the intermolecular interactions involved has been obtained through single-crystal X-ray studies of tweezer complexes with model diimides. Ring-current magnetic shielding of polyimide protons by the pyrene '' arms '' of the tweezer molecule induces large complexation shifts of the corresponding H-1 NMR resonances, enabling specific triplet sequences to be identified by their complexation shifts. Extended comonomer sequences (triplets of triplets in which the monomer residues differ only by the presence or absence of a methyl group) can be '' read '' by a mechanism which involves multiple binding of tweezer molecules to adjacent diimide residues within the copolymer chain. The adjacent-binding model for sequence recognition has been validated by two conceptually different sets of tweezer binding experiments. One approach compares sequence-recognition events for copolyimides having either restricted or unrestricted triple-triplet sequences, and the other makes use of copolymers containing both strongly binding and completely nonbinding diimide residues. In all cases the nature and relative proportions of triple-triplet sequences predicted by the adjacent-binding model are fully consistent with the observed H-1 NMR data.

Effect of headgroup size, charge, and solvent structure on polymer−micelle interactions, studied by molecular dynamics simulations

We performed atomistic molecular dynamics simulations of anionic and cationic micelles in the presence of poly(ethylene oxide) (PEO) to understand why nonionic water-soluble polymers such as PEO interact strongly with anionic micelles but only weakly with cationic micelles. Our micelles include sodium n-dodecyl sulfate (SDS), n-dodecyl trimethylammonium chloride (DTAC), n-dodecyl ammonium chloride (DAC), and micelles in which we artificially reverse the sign of partial charges in SDS and DTAC. We observe that the polymer interacts hydrophobically with anionic SDS but only weakly with cationic DTAC and DAC, in agreement with experiment. However, the polymer also interacts with the artificial anionic DTAC but fails to interact hydrophobically with the artificial cationic SDS, illustrating that large headgroup size does not explain the weak polymer interaction with cationic micelles. In addition, we observe through simulation that this preference for interaction with anionic micelles still exists in a dipolar "dumbbell" solvent, indicating that water structure and hydrogen bonding alone cannot explain this preferential interaction. Our simulations suggest that direct electrostatic interactions between the micelle and polymer explain the preference for interaction with anionic micelles, even though the polymer overall carries no net charge. This is possible given the asymmetric distribution of negative charges on smaller atoms and positive charges oil larger units in the polymer chain.

Multiple sol-gel transitions of PEG-PCL-PEG triblock copolymer aqueous solution

An aqueous solution of a poly(ethylene glycol)-polycaprolactone-poly(ethylene glycol) (PEG-PCL-PEG) with a composition of EG13CL23EG13 undergoes multiple transitions, from sol-to-gel (hard gel)-to-sol-to-gel (soft gel)-to-sol, in the concentration range 20.0∼35.0 wt.-%. Through dynamic mechanical analysis, UV-vis spectrophotometry, small angle X-ray scattering, differential scanning calorimetry, microcalorimetry and 13C NMR spectroscopy, the mechanism of these transitions was investigated. The hard gel and soft gel are distinguished by the crystalline and amorphous state of the PCL. The extent of PEG dehydration and the molecular motion of each block also played a critical role in the multiple transitions. This paper suggests a new mechanism for these multiple transitions driven by temperature changes.

In vitro micro-tuber initiation and dormancy in yam

Dormancy is a mechanism that regulates the timing of sprouting (germination) of affected plant parts as well as ensures that the food quality of edible parts is maintained in storage until the following growing season. In yam, however, little is known about the control of tuber initiation or tuber dormancy. The objective of this study was to determine the effects of selected plant growth regulators (PGRs) on tuber initiation and dormancy, using an in vitro system. In two replicated experiments, 2-chloroethylphosphonic acid (ethephon, an ethylene source), abscisic acid (ABA) and gibberellin (GA3) – and their inhibitors silver nitrate, fluridone and 2-chloroethyl-trimethylammonium chloride, respectively – were added at two concentrations to the culture medium prior to explant culture. Dates of micro-tuber initiation and sprouting (end of dormancy) and tuber number were recorded. In the control (no PGR) in Experiment 1, micro-tubers were initiated at the base of the stem after 176 days and sprouted 235 days later, that is 411 days after culturing. Most PGR treatments had only small effects (±30 days) on the duration of dormancy and the time of micro-tuber initiation. However, in GA3 micro-tuber initiation occurred after 76 days, about 100 days earlier than in the control, whereas fluridone affected the position of micro-tubers and duration of dormancy. With fluridone treatments, tubers were found at the base of the stem (normal position) and on lower and upper nodes. Lower node tubers sprouted within 225 days of culturing compared with about 420 days after culturing at other nodal positions and in other PGR treatments. These data suggest an important role for ABA and gibberellic acid in yam micro-tuber initiation and the induction of dormancy.

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.

Kinetics of layer hopping in a diblock copolymer lamellar phase

In the ordered state, symmetric diblock copolymers self-assemble into an anisotropic lamellar morphology. The equilibrium thickness of the lamellae is the result of a delicate balance between enthalpic and entropic energies, which can be tuned by controlling the temperature. Here we devise a simple yet powerful method of detecting tiny changes in the lamellar thickness using optical microscopy. From such measurements we characterize the enthalpic interaction as well as the kinetics of molecules as they hop from one layer to the next in order to adjust the lamellar thickness in response to a temperature jump. The resolution of the measurements facilitate a direct comparison to predictions from self-consistent field theory.

Modeling the tetraphenylalanine-PEG hybrid amphiphile: from DFT calculations on the peptide to molecular dynamics simulations on the conjugate

The conformational properties of the hybrid amphiphile formed by the conjugation of a hydrophobic peptide with four phenylalanine (Phe) residues and hydrophilic poly(ethylene glycol), have been investigated using quantum mechanical calculations and atomistic molecular dynamics simulations. The intrinsic conformational preferences of the peptide were examined using the building-up search procedure combined with B3LYP/ 6-31G(d) geometry optimizations, which led to the identification of 78, 78, and 92 minimum energy structures for the peptides containing one, two, and four Phe residues. These peptides tend to adopt regular organizations involving turn-like motifs that define ribbon or helicallike arrangements. Furthermore, calculations indicate that backbone ... side chain interactions involving the N-H of the amide groups and the pi clouds of the aromatic rings play a crucial role in Phe-containing peptides. On the other hand,MD simulations on the complete amphiphile in aqueous solution showed that the polymer fragment rapidly unfolds maximizing the contacts with the polar solvent, even though the hydrophobic peptide reduce the number of waters of hydration with respect to an individual polymer chain of equivalent molecular weight. In spite of the small effect of the peptide in the hydrodynamic properties of the polymer, we conclude that the two counterparts of the amphiphile tend to organize as independent modules.

Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2CH groups being orthogonal to this plane; 1 and 2 have the Rh–(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.