Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

Photoinduced conjugation of Dithioester- and Trithiocarbonate-Functional RAFT polymers with alkenes

We report the photoinduced conjugation of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by 1H NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI−MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast β-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.

Chain scission resists for extreme ultraviolet lithography based on high performance polysulfone-containing polymers

A series of polymers with a comb architecture were prepared where the poly(olefin sulfone) backbone was designed to be highly sensitive to extreme ultraviolet (EUV) radiation, while the well-defined poly(methyl methacrylate) (PMMA) arms were incorporated with the aim of increasing structural stability. It is hypothesized that upon EUV radiation rapid degradation of the polysulfone backbone will occur leaving behind the well-defined PMMA arms. The synthesized polymers were characterised and have had their performance as chain-scission EUV photoresists evaluated. It was found that all materials possess high sensitivity towards degradation by EUV radiation (E0 in the range 4–6 mJ cm−2). Selective degradation of the poly(1-pentene sulfone) backbone relative to the PMMA arms was demonstrated by mass spectrometry headspace analysis during EUV irradiation and by grazing-angle ATR-FTIR. EUV interference patterning has shown that materials are capable of resolving 30 nm 1:1 line:space features. The incorporation of PMMA was found to increase the structural integrity of the patterned features. Thus, it has been shown that terpolymer materials possessing a highly sensitive poly(olefin sulfone) backbone and PMMA arms are able to provide a tuneable materials platform for chain scission EUV resists. These materials have the potential to benefit applications that require nanopattering, such as computer chip manufacture and nano-MEMS.

Poly[aqua([mu]3-2-hydroxy-5-nitrobenzoato-[kappa]3O1:O1':O2)rubidium]

In the structure of title compound [Rb2(C7H4NO2)2(H2O)2]n the centrosymmetric cyclic dimeric repeating unit comprises two irregular RbO4 complex centres bridged by the carboxylate groups of the 5-nitrosalicylate ligands. The coordination about each Rb is completed by a monodentate water molecule and a phenolic O donor which gives a bridging extension [Rb-O range 3.116(7)-3.135(5)A]. The two-dimensional polymeric structure is stabilized by intermolecular water O-H...O(carboxyl) hydrogen bonds and weak inter-ring pi--pi interactions [minimum ring centroid separation, 3.620(4)A].

Pattern recognition using invariants defined from higher order spectra - one-dimensional inputs

A new approach to pattern recognition using invariant parameters based on higher order spectra is presented. In particular, invariant parameters derived from the bispectrum are used to classify one-dimensional shapes. The bispectrum, which is translation invariant, is integrated along straight lines passing through the origin in bifrequency space. The phase of the integrated bispectrum is shown to be scale and amplification invariant, as well. A minimal set of these invariants is selected as the feature vector for pattern classification, and a minimum distance classifier using a statistical distance measure is used to classify test patterns. The classification technique is shown to distinguish two similar, but different bolts given their one-dimensional profiles. Pattern recognition using higher order spectral invariants is fast, suited for parallel implementation, and has high immunity to additive Gaussian noise. Simulation results show very high classification accuracy, even for low signal-to-noise ratios.

Poly[tetra-mu-aqua-diaquatetrakis[mu-(E)-2-nitrocinnamato]tetrarubidium]

In the structure of the title compound [Rb4(C9H6NO4)4(H~2~O)6]n, the asymmetric unit comprises four rubidium complex cations, two of which have an RbO7 coordination polyhedron with a monocapped distorted octahedral stereochemistry and two of which have a distorted RbO6 octahedral coordination. The bonding about both the seven-coordinate centres is similar, comprising one monodentate water molecule together with three bridging water molecules and three carboxylate O-atom donors, two of which are bridging. The environments about the six-coordinate cations are also similar, comprising a monodentate nitro O-atom donor, a bridging water molecule and four bridging carboxylate O-atom donors [overall Rb-O range, 2.849(2)-3.190(2)A]. The coordination leads to a two-dimensional polymeric structure extending parallel to (001), which is stabilized by interlayer water O-H...O hydrogen-bonding associations to water, carboxyl and nitro O-atom acceptors, together with weak inter-ring pi--pi interactions [minimum ring centroid separation = 3.5319(19)A].