Solid phases of cyclopentane: combined experimental and simulation study

The phase diagram of cyclopentane has been studied by powder neutron diffraction, providing diffraction patterns for phases I, II, and III, over a range of temperatures and pressures. The putative phase IV was not observed. The structure of the ordered phase III has been solved by single-crystal diffraction. Computational modeling reveals that there are many equienergetic ordered structures for cyclopentane within a small energy range. Molecular dynamics simulations reproduce the structures and diffraction patterns for phases I and III and also show an intermediate disordered phase, which is used to interpret phase II.

Highly asymmetric phase diagram of a poly(1,2-octylene oxide)-poly(ethylene oxide) diblock copolymer system comprising a brush-like poly(1,2-octylene oxide) block

The phase diagram of a series of poly(1,2-octylene oxide)-poly(ethylene oxide) (POO-PEO) diblock copolymers is determined by small-angle X-ray scattering. The Flory-Huggins interaction parameter was measured by small-angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non-lamellar phases (hexagonal and gyroid) are observed near f(PEO) = 0.5, and the lamellar phase is observed for f(PEO) >= 0.5.

Multiple phases of North African humidity recorded in lacustrine sediments from the Fazzan Basin, Libyan Sahara

The Fazzan Basin of south-west Libya is at present arid with less than 20 mm of rainfall per annum. However, regionally extensive limestones, lacustrine sands and coquina (fossiliferous carbonate rock) deposits show that the Fazzan Basin previously contained a large palaeolake, indicating that the climate in the past was more humid. Optically stimulated luminescence (OSL) dating techniques have been applied to key lacustrine deposits within the basin in an attempt to provide an internally consistent chronology for this humidity record. Results indicate that palaeolake sediments within the Fazzan Basin record a very long history of palacohydrological change, ranging from present day and conditions to humidity capable of sustaining a lake with an approximate area of 76,250 km(2). The existence of humid periods in mid oxygen isotope stage 5 and the early Holocene is confirmed. An older lacustrine event, tentatively correlated to oxygen isotope stage 11, is also recognized. In addition, evidence is presented for at least two humid phases beyond the age range over which the conventional OSL dating technique is applicable. This study demonstrates that OSL dating of palaeolake sediments within the Fazzan Basin offers the potential to provide a detailed record of North African humidity spanning several glacial-interglacial cycles. (c) 2006 Elsevier Ltd. All rights reserved.

Subglacial bedform evidence for a major palaeo-ice stream and its retreat phases in Amundsen Gulf, Canadian Arctic Archipelago

Ascertaining the location of palaeo-ice streams is crucial in order to produce accurate reconstructions of palaeo-ice sheets and examine interactions with the ocean-climate system. This paper reports evidence for a major ice stream in Amundsen Gulf, Canadian Arctic Archipelago. Mapping from satellite imagery (Landsat ETM+) and digital elevation models, including bathymetric data, is used to reconstruct flow-patterns on southwestern Victoria Island and the adjacent mainland (Nunavut and Northwest Territories). Several flow-sets indicative of ice streaming are found feeding into the marine trough and cross-cutting relationships between these flow-sets (and utilising previously published radiocarbon dates) reveal several phases of ice stream activity centred in Amundsen Gulf and Dolphin and Union Strait. A large erosional footprint on the continental shelf indicates that the ice stream (ca. 1000 km long and ca. 150 km wide) filled Amundsen Gulf, probably at the Last Glacial Maximum. Subsequent to this, the ice stream reorganised as the margin retreated back along the marine trough, eventually splitting into two separate low-gradient lobes in Prince Albert Sound and Dolphin and Union Strait. The location of this major ice stream holds important implications for ice sheet-ocean interactions and specifically, the development of Arctic Ocean ice shelves and the delivery of icebergs into the western Arctic Ocean during the late Pleistocene. Copyright (C) 2006 John Wiley & Sons, Ltd.

Monte Carlo phase diagram for diblock copolymer melts

A partial phase diagram is constructed for diblock copolymer melts using lattice-based Monte Carlo simulations. This is done by locating the order-disorder transition (ODT) with the aid of a recently proposed order parameter and identifying the ordered phase over a wide range of copolymer compositions (0.2 <= f <= 0.8). Consistent with experiments, the disordered phase is found to exhibit direct first-order transitions to each of the ordered morphologies. This includes the spontaneous formation of a perforated-lamellar phase, which presumably forms in place of the gyroid morphology due to finite-size and/or nonequilibrium effects. Also included in our study is a detailed examination of disordered cylinder-forming (f=0.3) diblock copolymers, revealing a substantial degree of pretransitional chain stretching and short-range order that set in well before the ODT, as observed previously in analogous studies on lamellar-forming (f=0.5) molecules. (c) 2006 American Institute of Physics.

Monte Carlo phase diagram for diblock copolymer melts

The phase diagram for diblock copolymer melts is evaluated from lattice-based Monte Carlo simulations using parallel tempering, improving upon earlier simulations that used sequential temperature scans. This new approach locates the order-disorder transition (ODT) far more accurately by the occurrence of a sharp spike in the heat capacity. The present study also performs a more thorough investigation of finite-size effects, which reveals that the gyroid (G) morphology spontaneously forms in place of the perforated-lamellar (PL) phase identified in the earlier study. Nevertheless, there still remains a small region where the PL phase appears to be stable. Interestingly, the lamellar (L) phase next to this region exhibits a small population of transient perforations, which may explain previous scattering experiments suggesting a modulated-lamellar (ML) phase.

Phases of dormancy in yam tubers (Dioscorea rotundata)

center dot Background and Aims The control of dormancy in yam (Disocorea spp.) tubers is poorly understood and attempts to shorten the long dormant period (i.e. cause tubers to sprout or germinate much earlier) have been unsuccessful. The aim of this study was to identify and define the phases of dormancy in Dioscorea rotundata tubers, and to produce a framework within which dormancy can be more effectively studied. center dot Methods Plants of 'TDr 131' derived from tissue culture were grown in a glasshouse simulating temperature and photoperiod at Ibadan (7 degrees N), Nigeria to produce tubers. Tubers were sampled on four occasions: 30 d before shoot senescence (149 days after planting, DAP), at shoot senescence (179 DAP), and twice during storage at a constant 25 degrees C (269 and 326 DAP). The development of the apical shoot bud was described from tissue sections. In addition, the responsiveness of shoot apical bud development to plant growth regulators (gibberellic acid, 2-chloroethanol and thiourea) applied to excised tuber sections was also examined 6 and 12 d after treatment. center dot Key Results and Conclusions Three phases of tuber dormancy are proposed: Phase I, from tuber initiation to the appearance of the tuber germinating meristem; Phase II, from the tuber germinating meristem to initiation of foliar primordium; and Phase III, from foliar primordium to appearance of the shoot bud on the surface of the tuber. Phase I is the longest phase (approx. 220 d in 'TDr 131'), is not affected by PGRs and is proposed to be an endo-dormant phase. Phases II and III are shorter (< 70 d in total), are influenced by PGRs and environmental conditions, and are therefore endo-/eco-dormant phases. To manipulate dormancy to allow off-season planting and more than one generation per year requires that the duration of Phase I is shortened.

Phases of dormancy in yam tubers (Dioscorea rotundata)

Background and Aims The control of dormancy in yam (Disocorea spp.) tubers is poorly understood and attempts to shorten the long dormant period (i.e. cause tubers to sprout or germinate much earlier) have been unsuccessful. The aim of this study was to identify and define the phases of dormancy in Dioscorea rotundata tubers, and to produce a framework within which dormancy can be more effectively studied. center dot Methods Plants of 'TDr 131' derived from tissue culture were grown in a glasshouse simulating temperature and photoperiod at Ibadan (7 degrees N), Nigeria to produce tubers. Tubers were sampled on four occasions: 30 d before shoot senescence (149 days after planting, DAP), at shoot senescence (179 DAP), and twice during storage at a constant 25 degrees C (269 and 326 DAP). The development of the apical shoot bud was described from tissue sections. In addition, the responsiveness of shoot apical bud development to plant growth regulators (gibberellic acid, 2-chloroethanol and thiourea) applied to excised tuber sections was also examined 6 and 12 d after treatment. center dot Key Results and Conclusions Three phases of tuber dormancy are proposed: Phase I, from tuber initiation to the appearance of the tuber germinating meristem; Phase II, from the tuber germinating meristem to initiation of foliar primordium; and Phase III, from foliar primordium to appearance of the shoot bud on the surface of the tuber. Phase I is the longest phase (approx. 220 d in 'TDr 131'), is not affected by PGRs and is proposed to be an endo-dormant phase. Phases II and III are shorter (< 70 d in total), are influenced by PGRs and environmental conditions, and are therefore endo-/eco-dormant phases. To manipulate dormancy to allow off-season planting and more than one generation per year requires that the duration of Phase I is shortened.

Development of novel brush-type chiral stationary phases based on terpenoid selectors: HPLC evaluation and theoretical investigation of enantioselective binding interactions

The terpenoid chiral selectors dehydroabietic acid, 12,14-dinitrodehydroabietic acid and friedelin have been covalently linked to silica gel yielding three chiral stationary phases CSP 1, CSP 2 and CSP 3, respectively. The enantiodiscriminating capability of each one of these phases was evaluated by HPLC with four families of chiral aromatic compounds composed of alcohols, amines, phenylalanine and tryptophan amino acid derivatives and beta-lactams. The CSP 3 phase, containing a selector with a large friedelane backbone is particularly suitable for resolving free alcohols and their derivatives bearing fluorine substituents, while CSP 2 with a dehydroabietic architecture is the only phase that efficiently discriminates 1, 1'-binaphthol atropisomers. CSP 3 also gives efficient resolution of the free amines. All three phases resolve well the racemates of N-trifluoracetyl and N-3,5-dinitrobenzoyl phenylalanine amino acid ester derivatives. Good enantioseparation of beta-lactams and N-benzoyl tryptophan amino acid derivatives was achieved on CSP 1. In order to understand the structural factors that govern the chiral molecular recognition ability of these phases, molecular dynamics simulations were carried out in the gas phase with binary diastereomeric complexes formed by the selectors of CSP 1 and CSP 2 and several amino acid derivatives. Decomposition of molecular mechanics energies shows that van der Waals interactions dominate the formation of the diastereomeric transient complexes while the electrostatic binding interactions are primarily responsible for the enantioselective binding of the (R)- and (S)-analytes. Analysis of the hydrogen bonds shows that electrostatic interactions are mainly associated with the formation of N-(HO)-O-...=C enantio selective hydrogen bonds between the amide binding sites from the selectors and the carbonyl groups of the analytes. The role of mobile phase polarity, a mixture of n-hexane and propan-2-ol in different ratios, was also evaluated through molecular dynamics simulations in explicit solvent. (c) 2006 Elsevier Ltd. All rights reserved.

Structure, rheology and shear alignment of Pluronic block copolymer mixtures

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, Clue to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions Of Cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus Cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression. (C) 2008 Elsevier Inc. All rights reserved.

Formation of crystalline macrocyclic phases during electrophilic precipitation-polycondensation syntheses of poly(arylene ether ketone)s

Elongated crystalline particles formed as by-products during poly(arylene ether ketone) synthesis by electrophilic precipitation-polycondensation of 4,4'-diphenoxybenzophenone with terephthaloyl chloride or isophthaloyl chloride, thought previously to be polymer-whiskers, have now been identified as macrocyclic phases. Single crystal X-ray analysis of the needle-like particles formed in the reaction with terephthaloyl chloride, using the microdiffraction technique with synchrotron radiation, revealed that they consist of a macrocylic compound containing ten phenylene units, i.e. the [2 + 2] cyclic dimer. An analogous structure has also been demonstrated for the corresponding macrocycle derived from the reaction of 4,4-diphenoxybenzophenone with isophthaloyl chloride. Chloroform extraction of the products of the two polycondensations dissolved the macrocyclic material (but not the linear polymer), and analysis of the extracts by MALDI-TOF mass spectrometry demonstrated the presence in both cases of homologous families of macrocyclic products. Higher yields of macrocycles were obtained under pseudo-high dilution conditions, enabling the [2 + 2] cyclodimers from reactions of 4,4'-diphenoxybenzophenone with both terephthaloyl and isophthaloyl chloride to be isolated as pure compounds and fully characterised. (C) 2003 Published by Elsevier Ltd.

Melt brushes of diblock copolymer

Using self-consistent field theory (SCFT), we investigate the morphologies formed by a melt brush of AB diblock copolymers grafted to a flat substrate by their B ends. In addition to a laterally uniform morphology, SCFT predicts three ordered morphologies exhibiting different periodic patterns at the air surface: a hexagonal array of A-rich dots, an alternating sequence of A- and B-rich stripes, and a hexagonal pattern of B-rich dots. When the phase diagram of the tethered film is plotted as a function of A/B incompatibility, $\chi N$, and diblock composition, $f$, it resembles the bulk phase diagram with the periodic phases converging to a mean-field critical point at weak segregation. The periodic-phase region in the phase diagram shrinks with increasing grafting density and expands when the air surface acquires an affinity for the grafted B blocks.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.