Reversible polymerization driven by folding

Bisfunctionalized m-phenylene ethynylene imine oligomers were polymerized in the polar solvent acetonitrile, resulting in high-molecular weight poly(m-phenylene ethynylene imine)s. It is hypothesized that this polymerization, which proceeds through the reversible metathesis of imine bonds, is driven by the folding of the long m-phenylene ethynylene imine chains. Upon conducting the polymerization in a series of solvents in which the m-phenylene ethynylene oligomers exhibit different folding stabilities, it was possible to correlate the molecular weight of the resulting poly(m-phenylene ethynylene imine)s with the helical stability of the corresponding oligomers. The polymerization was also demonstrated to be reversible and responsive to solvent and temperature changes.     

Helical pitch of m-phenylene ethynylene foldamers by double spin labeling

To investigate the helical conformation of oligo(m-phenylene ethynylene)s, a pair of TEMPO spin labels were appended to the backbone. The two TEMPO radicals were separated by the four, five, and six repeating units. ESR spectra of the labeled oligomers were measured in chloroform and in ethyl acetate solvents in which the oligomers are disordered and folded, respectively. The measurement and analysis of ESR spectra revealed that six repeating units make one helical turn.     

Supramolecular chelation based on folding

Crystallographic analysis revealed that pyridine-palladium complexation is a good geometric match to the m-phenylene ethynylene (mPE) repeat unit and thus could serve as a reversible linking group to join oligomer segments together. A series of pyridine-terminated mPE oligomers were then synthesized and found to coordinate with palladium dichloride to give complexes effectively twice the length of the free oligomers. A quantitative analysis of these coordination equilibria by isothermal calorimetry found the ability of the pyridine end-group to form a coordination complex corresponded with their ability to fold. Oligomers that were able to form complexes of sufficient length to fold showed positive cooperativity based on experimental determination of their association constants with a palladium ion. We suggest that the additional free energy of complexation for the folded oligomers is analogous to chelation by multidentate ligands, but here the "multidentate ligand" is held together by supramolecular rather than covalent bonds.     

Synthesis of new mono-functionalised tetrathiafulvalene derivatives by reactions of etrathiafulvalenyllithium with aldehydes and ketones: X-ray crystal structures of TTF-CMe(OH)Fc, TTF-CMe(OMe)Fc and TTF-CH(OMe)TTF (Fc = ferrocenyl)

Reactions of tetrathiafulvalenyllithium (TTF-Li) with a range of aldehydes and ketones have been explored for the first time, to provide an efficient route to mono-functionalised TTF derivatives of general formulae TTF-CH(OH)R (R = alkyl, phenyl, tetrathiafulvalenyl and ferrocenyl) and TTF-CR(OH)R′ (R = alkyl, phenyl, R′ = alkyl, phenyl, tetrathiafulvalenyl, ferrocenyl, and R-R′ = fluorenyl). Subsequent transformations involving the reactive alcohol group of some of these compounds are reported. The structures of the three title compounds have been established by single-crystal X-ray analysis.     

Solid-Phase Synthesis of Phenylacetylene Oligomers Utilizing a Novel 3-Propyl-3-(benzyl-supported) Triazene Linkage

Sequence-specific phenylacetylene oligomers consisting of functionalized monomers (hexyl benzoate, hexyl phenyl ether, benzonitrile, and tert-butylphenyl) are synthesized in gram quantities using solid-phase methods. Growing oligomers are attached to a divinylbenzene cross-linked polystyrene support by the 1-aryl-3-propyl-3-(benzyl-supported) triazene moiety. This linkage is obtained by reaction of arenediazonium tetrafluoroborate salts with a n-propylamino-modified Merrifield resin. Condensation strategies are described, producing oligomers with higher yields and simplified procedures compared to solution-phase methods. Terminal acetylene is protected with a trimethylsilyl group. After deprotection of the resin-bound terminal acetylene, an aryl iodide monomer or an aryl iodide-terminated oligomer is coupled to the supported oligomer using a palladium(0) catalyst. The cycle can be repeated to produce sequence-specific oligomers of varying length and functionality. The resulting oligomers are liberated from the polymer support by cleavage of the 1-aryl-3-propyl-3-(benzyl-supported) triazene group by reaction with iodomethane producing an aryl iodide.     

Synthesis of angular triquinanes from 1-Alkynylbicyclo[3.2. 0]hept-2-en-7-ones. A tandem alkoxy-cope ring Expansion/Transannular ring closure reaction

Addition of ethenyllithium reagents to the carbonyl group of dialkyl squarate-derived 1-alkynylbicyclo[3.2.0]hept-2-ene-7-ones (15), followed by a TBAF workup, results in a low-temperature anion-accelerated alkoxy-Cope rearrangement which proceeds by way of a strained cyclic allene intermediates (e.g.,17). This leads to the formation of angularly fused triquinanes (e.g., 20) in which each of the rings is functionally differentiated. Bicyclo[6.3. 0]undecadienones (e.g., 36) are the major products when the reactions are quenched with aqueous bicarbonate rather than TBAF. Under analogous conditions 2-alkylidene-1-alkynylbicyclo[3.2. 0]heptan-7-ones also give bicyclo[6.3.0]undecadienones by a mechanism that was established to involve a 1,5-hydrgen shift in a strained allene intermediate. The synthetic scope and mechanism of these and related transformations are discussed.     

Oxidation processes in blue water pipe

The thermal, hydrolytic and photochemical oxidation of blue water pipe material has been studied using Fourier Transform infra-red microscopy, differential scanning calorimetry (DSC) and hydroperoxide analysis. The results indicate that oxidation of the pipe occurs predominantly on the outer surface and to a lesser extent on the bore, often with little or no change in the middle layers, FTIR analysis of microtomed sections of the pipe supports the DSC analysis (oxidation induction time at 200°C—OIT) and indicates leaching and consumption of the polymer antioxidants at the outer surface of the pipe. Oxidation profiles at 80°C in water, as measured using carbonyl index, indicate an unusual hydrolytic oxidation and extraction of the carbonylic oxidation products only at the outer pipe surface to a depth of about 0·5 mm resulting in high hydroperoxidation levels. These oxidation analyses are consistent with density profile changes through the pipe wall. Whilst water is concluded to have an important influence in controlling pipe stability, which, in turn, is governed by the temperature and extractability of the polymer antioxidants, ultraviolet light is also seen to have a similar detrimental effect. The influence of these various degradative parameters on the long-term stability of pipe is discussed with a view to elucidating the mechanisms involved.     

PHOTOSENSITIZATION BY ANTIMALARIAL DRUGS

Abstract The antimalarial drugs, chloroquine, hydroxychloroquine, quinine, quinacrine, amodiaquine and primaquine and the local anaesthetic, dibucaine, were tested for in vitro photosensitizing capability by irradiation with 365 nm UV light in aqueous solutions. The ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran, histidine, tryptophan or xanthine, and to initiate the free radical polymerization of acrylamide was examined in the pH range 2-12. Chloroquine and hydroxychloroquine show maximal photooxidative behaviour when in the monocation form at pH 9, in contrast to quinine which is extremely efficient as the dication below pH 4. This pattern appears to relate to the fluorescence yield as a function of pH. Chloroquine in the monocation or neutral form was found to undergo dechlorination upon irradiation, and this correlates directly with its ability to initiate photo-polymerization of acrylamide. Quinine also gives rise to small polymerization rates, attributed to photo-ionization in the quinoline ring, yielding a cation radical. Amodiaquine, primaquine and quinacrine do not have significant photochemical activity in aqueous solution. Dibucaine exhibits a strong photosensitizing capability at low pH, similar to quinine.     

HEU measurements of holdup and recovered residue in the deactivation and decommission activities of the 321-M Reactor Fuel Fabrication Facility at the Savannah River Site

Summary This paper contains a summary of the holdup and material control and accountability (MC&A) assays conducted for the determination of highly enriched uranium (HEU) in the deactivation and decommissioning (D&D) of the Reactor Fuel Fabrication Facility at the Savannah River Site (SRS). The facility was used to fabricate HEU fuel assemblies, lithium-aluminum target tubes, neptunium assemblies, and miscellaneous components for the SRS production reactors. The facility operated for more than 35 years. During this time thousands of uranium-aluminum alloy (U-Al) production reactor fuel tubes were produced. After the facility ceased operations in 1995, all of the easily accessible U-Al was removed from the building, and only residual amounts remained. The bulk of this residue was located in the equipment that generated and handled small U-Al particles and in the exhaust systems for this equipment (e.g., chip compactor, casting furnaces, log saw, lathes A & B, cyclone separator, Freon?cart, riser crusher, …, etc). The D&D project is likely to represent an important example for D&D activities across SRS and across the Department of Energy weapons complex. The Savannah River National Laboratory was tasked to conduct holdup assays to quantify the amount of HEU on all components removed from the facility prior to placing in solid waste containers. The ²³⁵U holdup in any single component of process equipment must not exceed 50 g in order to meet the container limit. This limit was imposed to meet criticality requirements of the low level solid waste storage vaults. Thus, the holdup measurements were used as guidance to determine if further decontamination of equipment was needed to ensure that the quantity of ²³⁵U did not exceed the 50 g limit and to ensure that the waste met the Waste Acceptance Criteria (WAC) of the solid waste storage vaults. Since HEU is an accountable nuclear material, the holdupassays and assays of recovered residue were also important for material control and accountability purposes. In summary, the results of the holdup assays were essential for determining compliance with the Waste Acceptance Criteria, Material Control & Accountability, and to ensure that administrative criticality safety controls were not exceeded. This paper discusses theg-ray assay measurements conducted and the modeling of the acquired data to obtain measured holdup in process equipment, exhaust components, and fixed geometry scrap cans. It also presents development work required to model new acquisition configurations and to adapt available instrumentation to perform the assays.     

Microwave promoted amination of 3-bromoisoxazoles

This Letter describes the amination of 3-bromoisoxazoles by a nucleophilic aromatic substitution reaction. We have found 3-bromoisoxazoles to be inert to substitution under thermal conditions, however, the employment of phosphazene bases under microwave irradiation facilitates the amination process and allows the corresponding 3-aminoisoxazoles to be isolated in moderate yield.