Competitive hydrogen bonding and self-assembly in Poly(2-vinyl pyridine)-block-Poly(methyl methacrylate)/ Poly(hydroxyether of bisphenol A) blends

Blends of poly(2-vinyl pyridine)-block-poly(methyl methacrylate) (P2VP-b-PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP-b-PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self-assembled nanostructures of the P2VP-b-PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes.

Reactive block copolymer modified thermosets : highly ordered nanostructures and improved properties

A highly ordered poly(dimethyl siloxane)-poly(glycidyl methacrylate) (PDMS-PGMA) reactive diblock copolymer was synthesized and used to modify bisphenol A-type epoxy resin (ER). The PDMS-PGMA block copolymer consisted of epoxy-miscible PGMA blocks and an epoxy-immiscible PDMS block. The PGMA reactive block of the block copolymer formed covalent bonds with cured epoxy and was involved in the network formation, and the PDMS block phase separated to give different ordered and disordered nanostructures at different blend compositions. The solvent cast PDMS-PGMA diblock copolymer showed ordered hexagonal cylindrical morphology. A highly ordered morphology consisting of hexagonal cylinders inside the lamellar morphology was observed in the cured PDMS-PGMA block copolymer. In the cured ER/PDMS-PGMA blends, a variety of morphologies including lamellar, cubic and worm-like and spherical nanostructures were detected depending on the blend composition. Moreover, the addition of this reactive diblock copolymer significantly increases the hydrophobicity and the glass transition temperature. It also improves the tensile strength and tensile ductility of the nanostructured thermosets at low diblock copolymer contents.

Late Guadalupian (Middle Permian) Fusuline fauna from the Xiala formation in Xainza county, central Tibet : implication of the rifting time of the Lhasa Block

A fusuline fauna consisting of 9 species of 4 genera from the Xiala Formation of the Mujiucuo section, Xainza County, Tibet, China is described. The fusuline fauna is dominated by Nankinella and Chusenella and indicates a Midian (Late Guadalupian) age. The earliest record of fusuline fauna during the Midian in the Lhasa Block suggests that the block rifted later than the Qiangtang Block to the north and the Baoshan and Tengchong blocks to the east, all of which yield much earlier fusuline faunas of Yakhtashian (Artinskian) age, but had drifted away from Gondwana to a relatively warm temperate zone in the Late Guadalupian (Middle Permian).

The Lopingian series in the Lhasa Block, Tibet and its palaeogeographical implications

Latest investigation indicates that the Lopingian Series including both terrestrial and marine deposit s are developed in the Lhasa Block. The marine Lopinigian Series in the Lhasa Block contains the compound coral Waagenophyllum, fusulinid Reichelina, and foraminifer Colaniella faunas , and the terrestrial Lopingian Series is characterized by both Cathaysian floras and mixed floras consisting of Gondwanan element s such as Glossopteris , Noeggerathiopsis, Phyllotheca and Cathaysian elements such as Pecopteris ,Sphenopteris. An anlaysis of the Lopingian sequences in the Lhasa Block reveals that it experienced a regression stage f rom Guadalupian to Lopingian. By contrast , the Himalayan Tethys Zone south to the Lhasa Block is characterized by typical Gondwanan Glossopteris flora , coldwater brachiopod and solitary coral faunas. In addition, the Lopingian sequence in the Himalayan Tethys Zone reflect s a transgressive process from the terrestrial Qubu Formation to the shallow marine Qubuerga Formation. Therefore, the Lhasa Block shows significant differences in both biota and depositional features from the Himalayan Tethys Zone during the Lopingian, which implies that the Lhasa Block had rifted from the northern periGondwanan margin before the Lopingian.

Hydrogen bonded block copolymer systems : from microphase separation in solid state to self-assembly in aqueous solutions

Block copolymer systems with hydrogen bonding interactions have received relatively little attention. Recently, we have investigated the self-assembly and phase separation in such block copolymer systems with an attempt to elucidate the role of hydrogen bonding interactions both theoretically and experimentally [1-4]. In A-b-B/C diblock copolymer/homopolymer systems, the phase behavior was theoretically analyzed according to the random phase approximation and correlated with hydrogen bonding interactions in terms of the difference in inter-association constants (K). To examine how the hydrogen bonding determines the self-assembly and morphological transitions in these systems, we have introduced the K values as a new variable into the phase diagram which we established for the first time (Fig. 1). Multiple vesicular morphologies were formed in aqueous solution of A-b-B/A-b-C diblock copolymer complexes of PS-b-PAA and PS-b-PEO. Interconnected compound vesicles (ICCVs) were observed for the first time as a new morphology (Fig. 2), along with other aggregated nanostructures including vesicles, multilamellar vesicles, thick-walled vesicles and irregular aggregates. Complexation of two amphiphilic diblock copolymers provides a viable approach to vesicles in aqueous media.

Microphase separation in double crystalline poly (ethylene oxide)-block-poly (caprolactone)/poly (4-vinyl phenol) blends

We report microphase separation induced by competitive hydrogen bonding interactions in double crystalline diblock copolymer/homopolymer blends of poly(ethylene oxide)-block-poly(ɛ-caprolactone) (PEO-b-PCL) and poly(4-vinyl phenol) (PVPh). The diblock copolymer PEO-b-PCL consists of two immiscible crystallizable blocks wherein both PEO and PCL blocks can form hydrogen bonds with PVPh. In these A-b-B/C diblock copolymer/homopolymer blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically PVPh and PEO block interact strongly whereas PVPh and PCL block interact weakly. The TEM and SAXS results show that the cubic PEO-b-PCL diblock copolymer changes into ordered hexagonal cylindrical morphology upon addition of 20 wt % PVPh followed by disordered bicontinuous phase in the blend with 40 wt % PVPh and then to homogenous phase at 60 wt% PVPh and above. Up to 40 wt % PVPh there is only weak interaction between PVPh and PCL due to the selective hydrogen bonding between PVPh and PEO. However, with higher PVPh concentration, the blends become homogeneous since a sufficient amount of PVPh is available to form hydrogen bonds with both PEO and PCL. A structural model was proposed to explain the self-assembly and morphology of these blends based on the experimental results obtained. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen bonding interaction between each block of the block copolymer and the homopolymer (1-3).

Femoral neck geometry and hip fracture risk : the Geelong Osteoporosis Study

To determine the relationship between femoral neck geometry and the risk of hip fracture in post-menopausal Caucasian women, we conducted a retrospective study comparing the femoral neck dimensions of 62 hip fracture cases to those of 608 randomly selected controls. Measurements were made from dual-energy X-ray absorptiometry scans (Lunar DPX-L), using the manufacturers ruler function, and included: hip axis length (HAL), femoral neck axis length (FNAL), femoral neck width (FNW), femoral shaft width (FSW), medial femoral shaft cortical thickness (FSCT_med), and lateral femoral shaft cortical thickness (FSCT_lat). The fracture group was older (median age 78.3 years vs 73.8 years), lighter (median weight 59.9 kg vs 64.5 kg), and, after adjustment for age, taller (mean height 158.7±0.8 cm vs 156.7±0.2 cm) than the controls. Furthermore, bone mineral density was lower in this group (0.682±0.016 g/cm² vs 0.791±0.006 g/cm²). After adjustment for age, bone mineral content (BMC) or height, hip fracture patients had greater FNW (up to 6.6%) and FSW (up to 6.3%) than did the controls. Each standard deviation increase in FNW and FSW was associated with a 1.7-fold (95% CI 1.3–2.3) and a 2.4-fold (95% CI 1.8–3.2) increase in the fracture risk, respectively. BMC-adjusted FNAL was greater in the fracture group (+2.1%) than in the controls, while the age-adjusted FSCT_med was reduced (–7.2%). There was a trend towards longer HAL (up to 2.1%) after adjustment for age or BMC, and thinner age-adjusted FSCT_lat (–1.7%) in fracture patients that did not reach statistical significance. In multivariate analysis, the risk of hip fracture was predicted by the combination of age, FNW, FSW, BMC and FSCT_med. HAL was not analyzed because of the small number of HAL measurements among fracture cases. We conclude that post-menopausal women with hip fractures have wider femoral necks and shafts, thinner femoral cortices and longer femoral neck axis lengths than do women with no fractures. Alteration in hip geometry is associated with the risk of hip fracture.

Femoral neck dimensions are unlikely to be associated with age at menarche

Hip axis length (HAL) has been reported as an independent risk factor for hip fracture. Later puberty may increase bone size because of delayed epiphyseal fusion. We sought to identify associations between bone size at the proximal femur with age at menarche and other indices of growth such as stature. Femoral neck dimensions were measured from dual-energy X-ray absorptiometry scans of the proximal femur in a random sample of 203 premenopausal Caucasian women (age 20–30 years). There were no associations between age at menarche and HAL, femoral axis length (FAL) or femoral neck width (FNW). Age at menarche was associated with height (r= 0.2, p= 0.02). Variations in HAL, FAL and FNW do not appear to be related to age at menarche.

A new route to nanostructured thermosets with block ionomer complexes

We report a novel approach to prepare nanostructured thermosets using block ionomer complexes. Neither block copolymer polystyrene-block-poly(ethylene-ran- butylene)-block-polystyrene (SEBS) nor block ionomer sulfonated SEBS (SSEBS) is miscible with diglycidyl ether of bisphenol A (DGEBA) type epoxy resin. It is thus surprising that the block ionomer complex of SSEBS with a tertiary amine-terminated poly(3-caprolactone) (PCL), denoted as SSEBS-c-PCL, can be used to prepare nanostructured epoxy thermosets. The block ionomer complex SSEBS-c-PCL is synthesized via neutralization of SSEBS with 3-dimethylamino- propylamine-terminated PCL. Sulfonation of SEBS yields the block ionomer SSEBS which is immiscible with epoxy. But the block ionomer complex SSEBS-c-PCL can be easily mixed with DGEBA. When the curing agent 4,4'-methylenedianiline (MDA) is added and the epoxy cures, the system retains the nanostructure. In cured epoxy thermosets containing up to 30 wt% SSEBS-c-PCL, the exclusion of the poly(ethylene-ran-butylene) (EB) phase forms spherical micro-domains surrounded by separated sulfonated polystyrene phase while the PCL side-chains of SSEBS-c-PCL are dissolved in the cured epoxy matrix. The spherical micro-domains are highly aggregated in the epoxy thermosets containing 40 and 50 wt% SSEBS-c-PCL. The existence of epoxy-miscible PCL side-chains in the block ionomer complex SSEBS-c-PCL avoids macro-phase separation. Hence, the block ionomer complex can act as an efficient modifier to achieve nanostructured epoxy thermosets.