Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710     

Sonogashira alkynylation of unprotected 8-brominated adenosines and guanosines: fluorescence properties of compact conjugated acetylenes containing a purine ring

A practical Sonogashira alkynylation protocol for the preparation of 8-alkynylated adenosines and guanosines has been developed. Protection of the sugar hydroxyl substituents is not required; protection hinders the purification of these products. A preliminary fluorescent study is reported, which shows that the presence of a substituent on the phenylene ring influences the fluorescent properties considerably, an outcome that could be utilized in biological applications.     

Experiences in Expert Systems

This paper describes some work carried out in the Scientific Research and Development Branch (SRDB) of the Home Office, intended to contribute to an overall aim of building up internal expertise in the field of expert systems. This was done by carrying out a number of pilot and demonstrator projects, two of which are described in some detail. The plan, which proved successful, was to build as far as possible on the relevant skills already possessed by an OR group in the branch. The lessons learned from these are summarized in the hope that they will be of use to other groups who wish to become involved in this important area.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

The combinatorics of the bar resolution in group cohomology

We study a combinatorially defined double complex structure on the ordered chains of any simplicial complex. Its columns are related to the cell complex K_n whose face poset is isomorphic to the subword ordering on words without repetition from an alphabet of size n. This complex is shellable and as an application we give a representation theoretic interpretation for derangement numbers and a related symmetric function considered by Désarménien and Wachs [11].

We analyze the two spectral sequences arising from the double complex in the case of the bar resolution for a group. This spectral sequence converges to the cohomology of the group and provides a method for computing group cohomology in terms of the cohomology of subgroups. Its behavior is influenced by the complex of oriented chains of the simplicial complex of finite subsets of the group, and we examine the Ext class of this complex.     

Electron transfer induced dissociations of 2- and 4-alkyl cyclohexadienones

Several 2- and 4-alkylcyclohexadienones were prepared and shown to accept electrons to produce ketyl radical anions that dissociated rapidly at room temperature to release carbon-centered radicals and an aromatic phenoxide type anion. In the PET process with benzyl-substituted cyclohexadienones, initiated with triethylamine, the benzyl radicals dimerised or abstracted an H-atom from solvent. In electrochemical reductions, and in reductions with alkali metals in liquid ammonia, the benzyl radicals were further reduced to anions.     

The classification of closed surfaces using colored graphs

A short graph theoretic proof of the classification of closed surfaces is given. The new proof has the feature that the symmetric canonical graphs for the surfaces do not correspond to the canonical polygons in the usual proof of the classification.