Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones

Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

Synthesis of strained macrocyclic biaryls for enthalpy-driven ring-opening polymerization

Polymerizable macrocyclic biarylene-ether-ketones and biarylene-ether-sulfones are accessible from linear, bis(chloro)-terminated oligomers via nickel-catalyzed, intramolecular coupling under pseudo-high-dilution conditions. Single-crystal X-ray analyses of the resulting cyclo-oligomers reveal extremely distorted and highly strained geometries, with 4,4 '-biphenylene units showing deviations of up to 70 degrees from linearity.

Spontaneous ring-opening polymerization of macrocyclic aromatic thioether ketones under transient high-temperature conditions

Spontaneous ring-opening polymerization of macrocyclic aromatic thioether ketones [-1,4-SC6H4CO-C6H4-](n) (n = 3 and 4), in which the thioether linkages are para to the ketone, occurs during rapid, transient heating to 480degreesC, to afford a soluble, semi-crystalline poly(thioether ketone) of high molar mass (eta(inh) > 1.0 dL . g(-1)). Corresponding macrocyclic ether ketone, and a macrocyclic thioether ether ketone in which the thioether linkage is para to the ether rather than to the ketone, show no evidence of polymerization under analogous conditions.

Thermo-responsive poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) block copolymers synthesized by RAFT polymerization: micellization and gelation

RAFT polymerization was used to prepare PMMA-b-PNIPAM copolymers. Two different chain transfer agents, tBDB and MCPDB, were used to mediate the sequential polymerizations. Micellar solutions and gels were prepared from the resulting copolymers in aqueous solution. When heated above T-c of PNIPAM (about 31 degrees C), DLS revealed that PNIPAM coronas collapsed, resulting in aggregation of the original micelles. The micellar gels underwent syneresis above T-c as water was expelled from the ordered gel structure, the lattice periodicity of which was determined by SANS. A large decrease in lattice spacing was observed above T-c. The gel became more viscoelastic at high temperature, as revealed by shear rheometry which showed a large increase in G".

Rapid, uncatalyzed ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s under dynamic heating conditions

Uncatalyzed, ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s (1-4) and mixtures (5) under dynamic heating conditions has been demonstrated for the first time. High-molecular-weight, film-forming products were obtained after heating of the macrocycles up to 480 degreesC, with a heating rate of 10-20 degreesC /min. Depending on the macrocyclic structure and heat treatment conditions, the polymers obtained were amorphous or semicrystalline, soluble or slightly crosslinked. NMR analyses of the soluble polymers revealed their linear, highly regular structure. According to NMR, DSC, and TGA studies, the polymers obtained do not contain any residual macrocycles. The polymers with thio-p-arylene moieties in the main chain were thermally stabile. The catalyzed ring opening polymerization of 5 carried out in diphenyl sulfone solution is also reported for comparison. Using quantum mechanical calculations of the ring opening of macrocycles, a reaction mechanism is suggested. Preparation of nanosized poly(thioether ketone) fibrils by a replication method is described.

Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M-n = 29,700g mol(-1) (M-PS = 9300 g mol(-1) M-PMMA = 20,100 g mol(-1), PD = 1.15, chi(PS) = 0.323, chi(PMMA) = 0.677) and M-n = 63,900 g mol(-1) (M-PS = 50,500 g mol(-1), M-PMMA = 13,400 g mol(-1), PD = 1.18, chi(PS) = 0.790, chi(PMMA) = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 degrees C for 24 h led to a change in surface structure.

Conserved hydrophobic clusters on the surface of the Caf1A usher C-terminal domain are important for F1 antigen assembly

The outer membrane usher protein Caf1A of the plague pathogen Yersinia pestis is responsible for the assembly of a major surface antigen, the F1 capsule. The F1 capsule is mainly formed by thin linear polymers of Caf1 (capsular antigen fraction 1) protein subunits. The Caf1A usher promotes polymerization of subunits and secretion of growing polymers to the cell surface. The usher monomer (811 aa, 90.5 kDa) consists of a large transmembrane β-barrel that forms a secretion channel and three soluble domains. The periplasmic N-terminal domain binds chaperone-subunit complexes supplying new subunits for the growing fiber. The middle domain, which is structurally similar to Caf1 and other fimbrial subunits, serves as a plug that regulates the permeability of the usher. Here we describe the identification, characterization, and crystal structure of the Caf1A usher C-terminal domain (Caf1A(C)). Caf1A(C) is shown to be a periplasmic domain with a seven-stranded β-barrel fold. Analysis of C-terminal truncation mutants of Caf1A demonstrated that the presence of Caf1A(C) is crucial for the function of the usher in vivo, but that it is not required for the initial binding of chaperone-subunit complexes to the usher. Two clusters of conserved hydrophobic residues on the surface of Caf1A(C) were found to be essential for the efficient assembly of surface polymers. These clusters are conserved between the FGL family and the FGS family of chaperone-usher systems.

Photopolymerization of Pluronic F127 diacrylate: a colloid-templated polymerization

Pluronic F127 diacrylate (F127DA) is a bifunctional acrylate and as such it should in principle produce macroscopically cross-linked materials; however, its photopolymerization in water does not lead to 3D-extended hydrogels. The main species present after photopolymerization appear to be cross-linked micelles, which indicates that the micellar morphology of F127DA has a template effect on the polymerization. The structural analogy causes the physical state of precursor and polymerized materials to be very similar for a wide range of concentrations (5–25% wt) and temperatures (10–37 °C). Also the long-range morphology of F127DA appears to have a template effect: samples photopolymerized in a micellar gel state and redispersed at high concentration (25% wt) show a long-range organization that depended on the concentration and therefore on the order of the precursor.

Palaeovegetation in China during the late Quaternary: Biome reconstructions based on a global scheme of plant functional types

Two previous reconstructions of palaeovegetation across the whole of China were performed using a simple classification of plant functional types (PFTs). Now a more explicit, global PFT classification scheme has been developed, and a substantial number of additional pollen records have become available. Here we apply the global scheme of PFTs to a comprehensive set of pollen records available from China to test the applicability of the global scheme of PFTs in China, and to obtain a well-founded reconstruction of changing palaeovegetation patterns. A total of 806 pollen surface samples, 188 mid-Holocene (MH, 6000 14C yr BP) and 50 last glacial maximum (LGM, 18,000 14C yr BP) pollen records were used to reconstruct vegetation patterns in China, based on a new global classification system of PFTs and a standard numerical technique for biome assignment (biomization). The biome reconstruction based on pollen surface samples showed convincing agreement with present potential natural vegetation. Coherent patterns of change in biome distribution between MH, LGM and present are observed. In the MH, cold and cool-temperate evergreen needleleaf forests and mixed forests, temperate deciduous broadleaf forest, and warm-temperate evergreen broadleaf and mixed forest in eastern China were shifted northward by 200–500 km. Cold-deciduous forest in northeastern China was replaced by cold evergreen needleleaf forest while in central northern China, cold-deciduous forest was present at some sites now occupied by temperate grassland and desert. The forest–grassland boundary was 200–300 km west of its present position. Temperate xerophytic shrubland, temperate grassland and desert covered a large area on the Tibetan Plateau, but the area of tundra was reduced. Treeline was 300–500 m higher than present in Tibet. These changes imply generally warmer winters, longer growing seasons and more precipitation during the MH. Westward shifts of the forest–shrubland–grassland and grassland–desert boundaries imply greater moisture availability in the MH, consistent with a stronger summer monsoon. During the LGM, in contrast, cold-deciduous forest, cool-temperate evergreen needleleaf forest, cool mixed forests, warm-temperate evergreen broadleaf and mixed forest in eastern China were displaced to the south by 300–1000 km, while temperate deciduous broadleaf forest, pure warm-temperate evergreen forest, tropical semi-evergreen and evergreen broadleaf forests were restricted or absent from the mainland of southern China, implying colder winters than present. Strong shifts of temperate xerophytic shrubland, temperate grassland and desert to the south and east in northern and western China and on the Tibetan Plateau imply drier conditions than present.

Ring-opening polymerization in molten PEEK: transient reduction of melt-viscosity by macrocyclic aromatic thioetherketones

Blends of PEEK with macrocyclic thioether-ketones show initial melt-viscosities reduced by more than an order of magnitude relative to the polymer itself, enabling more facile processing and fabrication. On raising the temperature of the melt, however, the macrocycle undergoes spontaneous, entropically-driven ring-opening polymerization (ED-ROP), so that the properties of the final polymer should not, in principle, be compromised by the presence of low-MW macrocyclic material.

The dependence of radiative forcing and feedback on evolving patterns of surface temperature change in climate models

Experiments with CO2 instantaneously quadrupled and then held constant are used to show that the relationship between the global-mean net heat input to the climate system and the global-mean surface-air-temperature change is nonlinear in Coupled Model Intercomparison Project phase 5 (CMIP5) Atmosphere-Ocean General Circulation Models (AOGCMs). The nonlinearity is shown to arise from a change in strength of climate feedbacks driven by an evolving pattern of surface warming. In 23 out of the 27 AOGCMs examined the climate feedback parameter becomes significantly (95% confidence) less negative – i.e. the effective climate sensitivity increases – as time passes. Cloud feedback parameters show the largest changes. In the AOGCM-mean approximately 60% of the change in feedback parameter comes from the topics (30N-30S). An important region involved is the tropical Pacific where the surface warming intensifies in the east after a few decades. The dependence of climate feedbacks on an evolving pattern of surface warming is confirmed using the HadGEM2 and HadCM3 atmosphere GCMs (AGCMs). With monthly evolving sea-surface-temperatures and sea-ice prescribed from its AOGCM counterpart each AGCM reproduces the time-varying feedbacks, but when a fixed pattern of warming is prescribed the radiative response is linear with global temperature change or nearly so. We also demonstrate that the regression and fixed-SST methods for evaluating effective radiative forcing are in principle different, because rapid SST adjustment when CO2 is changed can produce a pattern of surface temperature change with zero global mean but non-zero change in net radiation at the top of the atmosphere (~ -0.5 Wm-2 in HadCM3).