Molecular organization in the twist-bend nematic phase by resonant X-ray scattering at the Se K-edge and by SAXS, WAXS and GIXRD.

Using a magnetically aligned liquid crystal mixture containing a novel Se-labelled dimer and the difluoroterphenyl dimer DTC5C7, the twist-bend nematic phase (Ntb) was studied by the resonant scattering of hard X-rays and by conventional small and wide-angle X-ray scattering (SAXS, WAXS). Resonant diffraction spots indicated a helix with a 9-12 nm pitch in the Ntb phase and an unprecedentedly high helix orientation. This enabled deconvolution of global and local order parameters. These findings, combined with the simultaneously recorded resonant and non-resonant SAXS and WAXS data, allowed us to construct a locally layered molecular model of the Ntb phase, where the average twisted conformation of each molecule was idealised as a helical segment, matching the local heliconical director field. The dimers were found to be less bent in the Ntb phase than in their minimum energy conformation, and straightening further with increasing temperature. It is proposed that on further heating their low bend angle allows the transition to the normal nematic phase, where the molecules can freely move longitudinally, without the need to perform screw-like motion as in the Ntb phase. At the low-temperature end, the increasing molecular twist becomes unsustainable, leading to a transition to a smectic phase, where no twist is required.

Heavy metal accumulation and source analysis in greenhouse soils of Wuwei District, Gansu Province, China.

Greenhouse soils and arable (wheat field) soil samples were collected to identify the effects of greenhouse cultivation on the accumulation of six heavy metals (Cd, Cu, Zn, Pb, Cr, and Ni) and to evaluate the likely sources responsible for heavy metal accumulation in the irrigated desert soils of Wuwei District, China. The results indicated that the mean concentrations of Cd, Cu, Zn, Pb, Cr, and Ni were 0.421, 33.85, 85.31, 20.76, 53.12, and 28.59 mg kg(-1), respectively. The concentrations of Cd, Cu, and Zn in greenhouse soils were 60, 23, and 14% higher than those in arable soils and 263, 40, and 25% higher than background concentrations of natural soils in the study area, respectively. These results indicated that Cd, Cu, and Zn accumulation occurred in the greenhouse soils, and Cd was the most problematically accumulated heavy metal, followed by Cu and Zn. There was a significant positive correlation between the concentrations of Cd, Cu, and Zn in greenhouse soils and the number of years under cultivation (P < 0.05). Greenhouse cultivation had little impact on the accumulation of Cr, Ni, or Pb. Correlation analysis and principal component analysis suggested that the accumulation of Cd, Cu, and Zn in greenhouse soils resulted mainly from fertilizer applications. Our results indicated that the excessive and long-term use of fertilizers and livestock manures with high heavy metal levels leads to the accumulation of heavy metals in soils. Therefore, rational fertilization programs and reductions in the concentrations of heavy metals in both fertilizers and manure must be recommended to maintain a safe concentration of heavy metals in greenhouse soils.

Arsenate reduction and methylation in the cells of Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 investigated with X-ray absorption near edge structure.

Synchrotron radiation-based X-ray absorption near edge structure (XANES) was introduced to directly analysis chemical species of arsenic (As) in the cells of Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 capable of As accumulation and volatilisation. After exposure to As(V) of 500 mg L(-1) for 15 days, a total of 60.5% and 65.3% of the accumulated As in the cells of T. asperellum SM-12F1 and P. janthinellum SM-12F4, respectively, was As(III), followed by 31.3% and 32.4% DMA (dimethylarsinic acid), 8.3% and 2.3% MMA (monomethylarsonic acid), respectively. However, for F. oxysporum CZ-8F1, 54.5% of the accumulated As was As(III), followed by 37.8% MMA and 7.7% As(V). The reduction and methylation of As(V) formed As(III), MMA, and DMA as the primacy products, and the reduction of As(V) might be more easily processed than the methylation. These results will help to understanding the mechanisms of As detoxification and its future application in bioremediation.

Complex tiling patterns in liquid crystals.

In this account recent progress in enhancing the complexity of liquid crystal self-assembly is highlighted. The discussed superstructures are formed mainly by polyphilic T-shaped and X-shaped molecules composed of a rod-like core, tethered with glycerol units at both ends and flexible non-polar chain(s) in lateral position, but also related inverted molecular structures are considered. A series of honeycomb phases composed of polygonal cylinders ranging from triangular to hexagonal, followed by giant cylinder honeycombs is observed for ternary T-shaped polyphiles on increasing the size of the lateral chain(s). Increasing the chain size further leads to new modes of lamellar organization followed by three-dimensional and two-dimensional structures incorporating branched and non-branched axial rod-bundles. Grafting incompatible chains to opposite sides of the rod-like core leads to quaternary X-shaped polyphiles. These form liquid crystalline honeycombs where different cells are filled with different material. Projected on an Euclidian plane, all honeycomb phases can be described either by uniformly coloured Archimedean and Laves tiling patterns (T-shaped polyphiles) or as multi-colour tiling patterns (X-shaped polyphiles). It is shown that geometric frustration, combined with the tendency to segregate incompatible chains into different compartments and the need to find a periodic tiling pattern, leads to a significant increase in the complexity of soft self-assembly. Mixing of different chains greatly enhances the number of possible 'colours' and in this way, periodic structures comprising up to seven distinct compartments can be generated. Relations to biological self-assembly are discussed shortly.

Crystal-amorphous polymer interface studied by neutron and x-ray scattering on labeled binary ultralong alkanes.

The recently discovered stable semicrystalline phase in binary ultralong alkanes is studied by small-angle neutron and x-ray scattering. Either the shorter or the longer alkane has (CD2)11CD3 ends. It is confirmed that chains are tilted in the crystal layer and found that ca. seven end carbons of the shorter alkane are amorphous. It is also established that the longer chains protrude from the crystal at both ends and that their end groups are preferentially located in the middle of the amorphous layer, suggesting gradual dissipation of orientational order of the chains exiting the crystal.

Novel layered superstructures in mixed ultralong n-alkanes.

Two new types of layered structures were found in binary mixtures of n-alkanes ranging from C122H246 to C294H590. At high temperatures a semicrystalline form is the stable phase, having a regular structure of alternating crystalline and amorphous layers. The two long-chain compounds are mixed in the crystalline layers and the amorphous layers consist of the surplus length of the longer chains. At lower temperatures a reversible transition occurs to a triple layer superlattice structure with a periodicity of up to 50 nm. These two new phases allow the existence of binary solid solutions of chains with a length ratio of up to 1.7 and a chain length difference of 100 CH2 groups.

[Study on the relationship between PMI and the concentration of zincum and nickel in the vitreous humor of rabbit after death].

OBJECTIVE: To seek a exact method of estimating postmortem interval (PMI). METHODS: This study detected the concentration of zincum(Zn) and nickel(Ni) in vitreous humor of rabbit at hour 96 after death and explored the relationship between their concentration and PMI using a method ICP-MS. RESULTS: The concentration of Zn and Ni in vitreous humor of rabbit at hour 24 after death were related to PMI significantly; The formulae of the relationship between PMI and Zn concentrations is y = 0.1404x2 - 1.3351x + 3.8298 (within 24 h; R2 = 0.9202). The formula of the relationship between PMI and Ni concentrations is y = 0.0043x2 - 0.0596x + 0.2665(within 24 h; R2 = 0.9103). CONCLUSION: The concentration of Zn and Ni in vitreous humor of rabbit may be a reference indicator to estimate early PMI.