Modular domain structure: a biomimetic strategy for advanced polymeric materials

A long lasting challenge in polymer science is to design polymers that combine desired mechanical properties such as tensile strength, fracture toughness, and elasticity into one structure. A novel biomimetic modular polymer design is reported here to address this challenge. Following the molecular mechanism used in nature, modular polymers containing multiple loops were constructed by using precise and strong hydrogen bonding units. Single-molecule force-extension experiments revealed the sequential unfolding of loops as a chain is stretched. The excellent correlation between the single-molecule and the bulk properties successfully demonstrates our biomimetic concept of using modular domain structure to achieve advanced polymer properties.     

Neutron activation analysis of the NIST Bovine Serum Standard Reference Material using chemical separations

Summary The US National Institute of Standards and Technology is currently in the process of certifying a Bovine Serum Standard Reference Material. In addition to elements normally considered to be of clinical interest, a number of other elements, which are analytically more difficult to determine yet are of importance from either a nutritional or toxicological viewpoint, are being determined by a variety of analytical techniques. Neutron activation analysis in combination with appropriate pre- or post-irradiation chemical separations, has been used to determine many of these difficult elements.

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Neutronenaktivierungsanalyse des Standardreferenzmaterials NIST Bovine Serum mit Hilfe chemischer Trennungen

     

New derivatives of 4,4,5,5-tetramethyl-4,5-dihydro-1-H-imidazol-1-oxyl 3-oxide as monomers for polyradicals with special magnetic properties

The preparation of new derivatives of 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide as monomers for purely organic polymers with special magnetic properties is described. 3,5-Diethynylbenzaldehyde and 3,5-bis(trimethylsilylethynyl)benzaldehyde were converted to the corresponding 1,3-dihydroxy-4,4,5,5-tetramethylimidazolidine derivatives which were oxidized to stable nitronyl nitroxide radicals.     

THE VALIDATION OF A NEW VASCULAR DAMAGE ASSAY FOR PHOTODYNAMIC THERAPY AGENTS

Abstract— The therapeutic effect of photodynamic therapy (PDT: photodynamic sensitizer + light) is partly due to vascular damage. This report describes a new vascular photodamage assay for PDT agents and a validation of the assay. The method described here quantitates changes in tissue blood perfusion based on the relative amount of injected fluorescein dye in treated and untreated tissues. A specially designed fluorometer uses chopped monochromatic light from an argon laser as a source for exciting fluorescein fluorescence. The fluorescent light emitted from the tissue is collected by a six element fiberoptic array, filtered and delivered to a photodiode detector coupled to a phase-locked amplifier for conversion to a voltage signal for recording. This arrangement permits a rather simple, inexpensive construction and allows for the simultaneous use of the argon laser by other investigators.
The routine assay for characterizing a specific photosensitizer at a standard dose consists of the sequential allocation of eight mice to a set of different light doses designed to span the dose-response range of fluorescein fluorescence exclusion (measured 8–10 min after fluorescein injection). The assay validation experiment used an anionic photosensitizer, 2-[l-hexyloxyethyl]-2-devinyl pyropheophorbide-a at a dose of 0.4 μmol/kg. The parameter estimates (n = 34 mice) from fitting the standard Hill dose-response model to the data were: median fluorescence exclusion light dose FE₅₀= 275 ± 8.3 J/cm² and Hill sigmoidicity parameter m =−3.66 ± 0.28. Subsets of the full data set randomly selected to simulate a standard eight mice experiment yielded similar parameter estimates. The new assay provides reliable estimates of PDT vascular damage with a frugal sequential experimental design.     

Effect of zinc soaps of rubber seed oil (RSO) and/or epoxidised rubber seed oil (ERSO) on the thermal stability of PVC plastigels

Zinc soaps of rubber seed oil (RSO) and epoxidised rubber seed oil (ERSO) were prepared and their use as PVC stabilizers investigated. Characterization of Zn soaps of RSO prepared by different techniques and ERSO gave information on the purity, structure and thermal behaviour of these materials. From the analysis, the production of these materials for use in thermal stabilization of PVC would be optimized as their use greatly enhanced the stability of PVC as obtained from the conductivity measurements using the 763 PVC Thermomat. The minimum amount of HCl release was obtained for the samples with Zn soaps and ERSO indicating a synergistic effect. Zn soaps having Zn(OH)₂ stabilized PVC better than pure Zn soaps.     

THE USE OF BENZOPHENONE AS A PHOTOAFFINITY LABEL, LABELING IN p-BENZOYLPHENYLACETYL CHYMOTRYPSIN AT UNIT EFFICIENCY

Abstract— p -Benzoylphenylacetyl chymotrypsin, an acyl enzyme derivative containing the benzophenone group in the hydrophobic binding pocket, was prepared and is indefinitely stable at low pH. Photolysis of this covalent derivative leads to loss of enzymic activity and incorporation of the labeling group via formation of a second covalent bond. The efficiency of the photochemical processes is exceptionally high, producing 100% incorporation and at least 92% inactivation. Analysis of active site titration data for the photolyzed enzyme show that at least two different photochemical processes must be involved. Elimination of phosphorescence emission and reduction of UV absorption upon photolysis are consistent with initial hydrogen abstraction by benzophenone triplet state, followed by radical coupling, much as has been observed for the photoreaction of benzophenone with model systems. Photoaffinity labeling of chymotrypsin is also efficiently accomplished using two benzophenone derivatives which bind noncovalently to the enzyme's active site, although the rates of labeling are somewhat less than in the covalent complex.     

18O effects on the infrared spectrum and skeletal tunneling of tropolone

Infrared-absorption profiles observed for vibrational transitions of gaseous tropolone often show sharp Q branch peaks, some of them ultranarrow spikes, indicative of the band origins for vibrational state-specific spectral tunneling doublets. In this work oxygen isotope effects for two CH wagging fundamentals, the COH torsion fundamental, and the skeletal contortion fundamental are reported. They allow considerations to be given: (1) oxygen isotope effects on the vibrational frequencies and state-specific tunneling splittings; (2) the asymmetry offset of the potential-energy minima for 16O and 18O tropolone; and (3) additional details concerning previously proposed high J rotation-contortion resonances in the contortional fundamental. The new results help to characterize the skeletal contortion fundamental and support the joint participation of skeletal tunneling with H tunneling in the vibrational state-specific tautomerization processes of tropolone in its ground electronic state.     

The New Cesium Praseodymium Thiophosphate Cs3Pr5[PS4]6

Transparent platelet‐shaped green single crystals of the title compound were obtained by the reaction of cesium bromide, praseodymium, sulfur, and red phosphorus in the molar ratio 1:2:8:2 with an excess of CsBr as flux in evacuated silica ampoules at 950 °C for fourteen days. Cs₃Pr₅[PS₄]₆ crystallizes monoclinically in the space group C2/c (a = 1627.78(7), b = 1315.09(6), c = 2110.45(9) pm, β = 103.276(5)°; Z = 4). Its crystal structure is different from all the other alkali‐metal containing ortho‐thiophosphates of the lanthanides, since it is not possible to formulate a layer containing the praseodymium centered sulfur polyhedra ([PrS₈]^13—, d(Pr—S) = 286 — 307 pm) and the isolated [PS₄]^3— tetrahedra (d(P—S) = 202 — 207 pm, ?(S—P—S) = 104 — 106°). All these tetrahedra are edge‐sharing with the metal polyhedra to build up a framework instead. The coordination sphere of the half occupied (Cs2)⁺ cations (CN = 10 + 2) can be described as two six‐membered sulfur rings in chair conformation containing a “cesium‐pair” in the middle. In contrast the (Cs1)⁺ cations are surrounded in the not unusual configuration of tetracapped trigonal prisms (CN = 10, better 10 + 2 as well).     

Poly(glycoamidoamine)s: Cationic glycopolymers for DNA delivery

Polymer science is playing an exciting role in inspiring and advancing novel discoveries in the area of genetic drug delivery. Polymeric materials can be synthesized and chemically tailored to bind and compact nucleic acids into viral‐like nanoparticles termed polyplexes that can deliver genetic materials into cells. This article highlights our work in this area to synthesize and study a novel class of cationic glycopolymers that we have termed poly(glycoamidoamine)s (PGAAs). The design of these materials has been inspired by many previous works in the literature. Carbohydrate comonomers have been incorporated into these structures to lower the toxicity of the delivery vehicle, and oligoamine moieties have been added to yield a cationic backbone that facilitates strong DNA binding, compaction, cellular uptake, and delivery of genetic material. PGAAs have been designed to vary in the carbohydrate size, the hydroxyl number and stereochemistry, the amine number, and the presence or absence of heterocyclic groups. Through structure–bioactivity studies, we have discovered that these materials are highly biocompatible, and each specific feature plays a large role in the observed delivery efficacy. Such structure–property studies are important for increasing our understanding of how the polymer chemistry affects the biological activity for the clinical development of polymer‐based therapeutics. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6895–6908, 2006