In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

Molecular and supramolecular deformations and disclinations in a liquid crystalline copolyether thin films under an electrostatic field

An alignment study of a liquid crystalline copolyether TPP-7/11(5/5) thin films has been carried out in a 10 kV . cm(-1) electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two-dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation, Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = pi /4 and defect walls form. These s = 1 disclinations possesses both left- and right-handednesses. Discussion of the defect formations have been attempted.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Structural and magnetic properties of (PrxSm1-x)Mn2Si2

Crystallographic and magnetic properties of intermetallic compounds (PrxSm1-x) Mn2Si2 (x = 0 similar to 0.80) have been investigated by X-ray powder diffraction, XPS and magnetic measurements. All the compounds crystallize in ThCr2Si2-type structure. Substitution of Pr for Sm leads to the increase of the lattice constants and the transition from antiferromagnetism (AFM) to ferromagnetism (FM). The valence-fluctuation in the compounds was observed and the relation between the change of electron binding energy and magnetic properties was also discussed preliminarily.

Rheological studies on the phase dissolution in a block copolymer

The microphase transition in a styrene-butadiene-styrene triblock copolymer was studied by rheometric mechanical spectroscopy. A high-temperature-melt rheological transition from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure was observed. The transition temperature is determined according to the discontinuity of the rheological properties across the transition region, which agrees well with the results obtained from the small angle X-ray scattering data and the expectation of the random phase approximation theory. Maybe for the first time, microphase dissolution was investigated theologically. The storage modulus (G') and the loss modulus (G '') increase with time during the process. An entanglement fluctuation model based on the segmental density fluctuations is presented to explain the rheological behavior in this dissolution process. (C) 1997 John Wiley & Sons.

MOLECULAR-GEOMETRY AND CHAIN ENTANGLEMENT - PARAMETERS FOR THE TUBE MODEL

The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimension is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, M(c), for the onset of entanglements is found to be M(c) = 28 A/([R2]0/M), where A is the chain cross-sectional area and [R2]0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, N(c) = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers.

THE CHARGE-DISTRIBUTION AND THE ELECTRIC-FIELD GRADIENT IN THE HIGH-TEMPERATURE SUPERCONDUCTOR TLBA2CAN-1CUNO2N+3 (N = 1 TO 3)

The net charges at atoms in the high-temperature superconductor TlBa2Can-1CunO2n+3 (n = 1 to 3) are calculated by means of the tight-binding approximation based on the EHMO method. The results indicate that the charge distribution in this kind of compounds possesses a specially layered arrangement. An insulating Ba-Ba layer is inserted between the Cu-O layer and the Tl-O layer. There may exist a weak coupling between the Cu-O layer and the Tl-O layer through the interaction of the same O(2) atom with both the Cu atom and the Tl atom. The existence of the Ca in the compounds can cause the valence fluctuation at the Cu atom. The calculated electric field gradients at atoms implies that the conducting electron or hole may move in the Cu-O layer, which is closest to the Tl-O layer, along the a-b plane.

A prophenoloxidase from the Chinese mitten crab Eriocheir sinensis: Gene cloning, expression and activity analysis

Prophenoloxidase (proPO) is a conserved copper-containing enzyme that plays important roles in immune response of crustaceans and insects. In the present study, the full-length cDNA of a prophenoloxidase (designated EsproPO) was cloned from haemocytes of Chinese mitten crab Eriocheir sinensis by expressed sequence tag (EST) and PCR techniques. The isolated 3549 bp full-length cDNA of EsproPO contained a 2040 bp open reading frame (ORF) encoding a putative proPO protein of 679 amino acids, a 5'-untranslated region (UTR) of 68 bp, and a long 3'-UTR of 1441 bp. Two putative copper-binding sites, a proteolytic activation site, and a complement-like motif (GCGWPQHM) were identified in the deduced amino acid sequence of EsproPO. Homology analysis revealed that EsproPO was highly similar to other proPOs from crustaceans with identities from 52% to 68%. The conserved domains and motifs, and higher similarity with other proPOs suggested that EsproPO was a member of the proPO family. The mRNA expression of EsproPO and PO specific activities in the tissues of hepatopancreas, gill, gonad, muscle, heart, eye and haemocytes were measured by quantitative real-time PCR and colorimetric assay, respectively. The mRNA transcripts of EsproPO and PO specific activities could be detected in all the examined tissues with the highest level both in hepatopancreas. Three peaks of EsproPO mRNA expression were recorded at 2 h, 12 h and 48 h in haemocytes of Chinese mitten crab post Vibrio anguillarum challenge, which was consistent with the temporal profile of PO specific activity. The mRNA expression pattern and the activity fluctuation of EsproPO post V. anguillarum stimulation indicated that it was potentially involved in the acute response against invading bacteria in Chinese mitten crab. (c) 2007 Elsevier Ltd. All rights reserved.

Cultivation of the brown alga Hizikia fusiformis (Harvey) Okamura: stress resistance of artificially raised young seedlings revealed by chlorophyll fluorescence measurement

Commercial farming of the intertidal brown alga Hizikia fusiformis (Harvey) Okamura in China and South Korea in the sea depends on three sources of seedlings: holdfast-derived regenerated seedlings, young plants from wild population and zygote-derived seedlings. Like many successfully farmed seaweed species, the sustainable development of Hizikia farming will rely on a stable supply of artificial seedlings via sexual reproduction under controlled conditions. However, the high rate of detachment of seedlings after transfer to open sea is one of the main obstacles, and has limited large-scale application of zygote-derived seedlings. To seek the optimal condition for growing seedlings on substratum in land-based tanks for avoidance of detachment in this investigation, young seedlings were grown in both outdoor tanks exposed directly to sunlight and in indoor raceway tanks in reduced, filtered sunlight. Results showed that young seedlings, immediately after fertilization, could withstand a daily fluctuation of direct solar irradiance up to a level of 1800 mu mol photons m(-1)s(-1), and maintained a faster growth rate than seedlings grown in indoor tanks. Detailed experiments by use of chlorophyll fluorescence measurements further demonstrated that the overnight (12 h) recovery of optimal fluorescence quantum yield (F-v/F-m) of seedlings after 1 h treatment at 40 degrees C was 98%, and the 48 h recovery of F-v/F-m of seedlings after 1 h exposure to 1800 mu mol m(-2)s(-1) was 92%. Forty-one-day-old seedlings showed no significant decrease of optimal fluorescence quantum yield at salinity ranging from 30 to 5 ppt for a treatment up to 17 h. Six-hour desiccation treatment did not have any influence on the optimal fluorescence quantum yield. Exposure to 18 mmol L-1 sodium hypochlorite for 10 min did not damage the PSII efficiency, and thus could be used to remove epiphytic algae. The strong tolerance of young seedlings to high temperature, high irradiance, low salinity and desiccation found in this investigation supports the view that mass production of Hizikia seedlings should be performed in ambient light and temperature instead of in shaded greenhouse tanks.

Recent 2000-year geological records of mud in the inner shelf of the East China Sea and their climatic implications

AXIS(14)C dating and grain-size analysis for Core DD2, located at the north of the Yangtze River-derived mud off the Zhejiang-Fujian coasts in the inner shelf of the East China Sea, provide us a high-resolution grain-size distribution curve varying with depth and time. Data in the upper mud layer of Core DD2 indicate that there are at least 9 abrupt grain-size increasing in recent 2000 years, with each corresponding very well with the low-temperature events in Chinese history, which might result from the periodical strengthening of the East Asian Winter Monsoon (EAWM), including the first-revealed maximum temperature lowering event at around 990 a BP. At the same time, the finer grain size section in Core DD2 agrees well with the Sui-Tang Warming Period (600-1000 a AD) defined previously by Zhu Kezhen, during which the climate had a warm, cold and warm fluctuation, with a dominated cooling period of 750-850 a AD. The Little Ice Age (LIA) can also be identified in the core. It starts around 1450 a AD and was followed by a subsequent cooling events at 1510, 1670 and 1840 a AD. Timing of these cold events revealed here still needs to be further verified owing to some current uncertainty of dating we used in this study.

Nd isotope as the tracer of seawater evolution of early Miocene in the eastern Pacific Ocean

Fifty-six samples of nannofossil ooze were collected from Core PC5794 in the northern equatorial Pacific at 5 em intervals. With the methods of mass spectrometer (VG354) and ICP, the Nd isotopic compositions (epsilon(Nd)(t)), Mn contents and Mg/Sr ratios of carbonate phase have been analyzed. CaCO3 contents of bulk sediments were obtained by dissolution of 0.5 mol/L HCl. Based on these data, the high-resolution epsilon(Nd)(t) profile of seawater in early Miocene with core depth(or time) have been established. The values of epsilon(Nd)(t) range from -6.2 to -2.97 and 4 fluctuation cycles existed during 24.06-22.02 Ma. 4 low epsilon(Nd)(t) values (about -6.4) correspond to high CaCO3 contents, which implicates that there were 4 cold epochs or 4 times of Antarctic Bottom Water activity. They occurred at the time of 24.06 Ma, 23.85 Ma, 22.88 Ma and 22.26 Ma, respectively. High epsilon(Nd)(t) values correspond to the high Mn contents and high values of Mg/Sr ratio, which indicates the existence of 4 intense hydrothermal activity periods during 24.06-22 Ma, the durations of them are 4.05-23.98 Ma, 23.69-23.15 Ma, 22.74-22.37 Ma and 22.06-22.02 Ma, respectively.

Geological records of marine environmental changes in the southern Okinawa Trough

Indexes of sediment grain size, sedimentation rates, geochemical composition, heavy minerals, benthic foraminiferal fauna, indicator species of the Kuroshio Current, paleo-SST and carbonate dissolution of core E017 conformably suggest a great marine environmental change occurring at about 10.1-9.2 cal. kaBP in the southern Okinawa Trough, which may correspond to the strengthening of the Kuroshio Warm Current and re-entering the Okinawa Trough through the sea area off northeast Taiwan. The invasion of Kuroshio current has experienced a process of gradual strengthening and then weakening, and its intensity became more fluctuation during the last 5000 years. Compared to the transition of sediment grain size, geochemical composition and heavy minerals, the foraminiferal faunas show a 900-year lag, which may indicate that the invasion of Kuroshio Current and the consequent sea surface and deep-water environmental changes is a gradual process, and fauna has an obvious lag compared to environment altering. The carbonate dissolution of the Okinawa Trough has had an apparent strengthening since 9.2 cal. kaBP, and reached a maximum in the late 3000 years, which may be caused by the deep-water environmental changes due to the invasion of Kuroshio Current.

History and variability of Asian interior aridity recorded by eolian flux in the Chinese Loess Plateau during the past 7 Ma

Eolian flux in the Chinese Loess Plateau was reconstructed by measuring the dry bulk density and CaCO3 content of the late Cenozoic loess-paleosol-red clay sequences in the Lingtai profile. Comparison of eolian flux variation between the Lingtai profile and the ODP sites 885/886 in the North Pacific shows a significant wet-dry variability in addition to a gradual drying trend in the dust source regions in interior Asia. Especially, the increase of eolian fluxes from both continental and pelagic eolian sediments indicates a sharp drying of the dust source regions between 3.6 and 2.6 MaBP, which might be attributed to the tectonic uplift of the Tibetan Plateau, which cut down the moisture input to the interior Asia. The average value and variability of eolian flux are higher after 2.6 MaBP than before, which may be related to the Quaternary climatic fluctuations on the glacial-interglacial timescale after the commencement of major Northern Hemisphere Glaciations. The eolian fluxes of the Lingtai profile and Core V21-146 in northwest Pacific show a synchronous variation on the 10(4)-10(5) a timescale, indicating that the flux variations from both continental and marine records are closely correlated to the Quaternary climatic fluctuation forced by the ice volume changes on a global scale.

Heinrich event imprints in the Okinawa Trough: evidence from oxygen isotope and planktonic foraminifera

Planktonic foraminiferal faunas, oxygen isotope and modern analog technique sea surface temperature records were obtained in piston core DGKS9603 (28degrees08.869'N, 127degrees16.238'E, water depth 1100 in) collected from the middle Okinawa Trough. During the last glaciation, four cold events were identified and correlate Heinrich events (HE) H2-5 of the last 45 ka. During the last deglaciation, core DGKS9603 has begun to be influenced by the Kuroshio since about 16 cal ka BP. Three weakenings of this warm current occurred at about 2.8-5.3, 11.4 and 15.5 cal ka BP respectively. Among the three fluctuations, the oldest one is synchronous with HE1 and could be a response to the strong cooling observed in the North Atlantic Ocean. The fluctuation occurring at about 11.4 cal ka ago corresponds to the Younger Dryas within the age error bars. Our observations provide new evidence that the HEs documented from Greenland and the northern North Atlantic had a global climatic impact. Changes in the intensity of the East Asian monsoon could be the main mechanism responsible for the paleoccanographic variations observed in the Okinawa Trough. (C) 2001 Elsevier Science B.V. All rights reserved.

Records of the East Asian winter monsoon from the mud area on the inner shelf of the East China Sea since the mid-Holocene

AMS(14)C dating and analysis of grain size, major elements and clay minerals were applied to Core MZ01 from the mud area on the inner shelf of the East China Sea. Based on the environmentally sensitive grain size, clay mineral and major element assemblages, the history of the East Asia winter monsoon since the mid-Holocene could be reconstructed. These three proxies, mean grain size (>9.71 mu m), chemical index of alteration (CIA) and ratio of smectite to kaolinite in particular, show similar fluctuation patterns. Furthermore, 10 extreme values corresponding to the contemporary cooling events could be recognized since the mid-Holocene; these extreme values are likely to have been caused by the strengthening of the East Asia winter monsoon. The cooling events correlated well with the results of the delta O-18 curves of the Dunde ice core and GISP2, which therefore revealed a regional response to global climate change. Four stages of the East Asia winter monsoon were identified, i.e. 8300-6300 a BP, strong and unstable; 6300-3800 a BP, strong but stable; 3800-1400 a BP, weak and unstable; after 1400 a BP, weak but stable.