胆甾侧链梳状聚合物液晶的合成、结构与性能研究

梳状聚合物液晶是八十年代迅速发展起来的一个新的研究课题，近几年来有不少科技工作者对其做了大量的研究工作。然而由于对它的研究尚为时不久，还不够深入，对其液晶相和结晶相的形成机理尚十分不清楚。另外，其结晶相和液晶相中分子的排列情况也不明确，这急待于深入地开展研究。本工作合成了以胆甾醇丙酸羟酯（羟乙和羟丙酯）为侧链以聚硅氧烷为主链的梳状聚合物PHECS-n和PHPCS-n和聚丙烯酸胆甾醇酯PACHE-n，利用DSC，偏光显微镜，电子显微镜，比旋光测定，变温红外光谱和x-ray衍射等手段对其相态行为，光学性质以及结晶形态和结晶结构进行了研究。相态行为的研究表明：PHECS-n和PHPCS-n是结晶性聚合物，在一定的温度范围内有明显的液晶结构存在，室温下是结晶的，对比PHECS-n、PHPCS-n和PACHE-n的相行为发现影响梳状聚合物液晶相行为的因素有聚合物的分子量，胆甾基因的含量和Spacer的柔性和长度。利用显微镜对PHECS-n和PHPCS-n结晶形态和结晶速度的研究发现胆甾含量和Spacer的柔性对结晶性能也有影响。首先，它们直接影响着其结晶的速度，随侧链含量减少和Spacer柔性的增加都明显增加其结晶速度。其次胆甾含量的不同也影响着其分子的排列方式，从而导致了PHECS-3和PHPCS-3所特有的周期性消光现象。利用变温红外光谱对各相态的分子光谱进行了研究。结果表明：液晶相与结晶相的分子排列不相同，液晶相的形成仅仅是由于胆甾基因的低维有取排列所致，聚合物主链对其有影响但无贡献，这初步明确了液晶相的形成机理。红外光谱的结果还表明：Spacer柔性仅仅影响其分子排列的易难程度，不影响分子的排列方式，这一新的结果对搞清液晶态的分子排列和形成机理有重要的理论和实际意义。首次对其晶态的x-ray研究给出了其晶态的晶胞参数和晶态的分子排列结构，这为进一步研究液晶相内分子的排列打下了基础。PACHE-n是非晶性聚合物，在室温下为玻璃态，在一定的条件能形成微弱的液晶结构，并能完整地冻结于玻璃态中，这为液晶聚合物在信息贮存方面的应用奠定了基础。

Improved surface morphology of stacked 1.3 mu m InAs/GaAs quantum dot active regions by introducing annealing processes

The authors report a simple but effective way to improve the surface morphology of stacked 1.3 mu m InAs/GaAs quantum dot (QD) active regions grown by metal-organic chemical vapor deposition (MOCVD), in which GaAs middle spacer and top separate confining heterostructure (SCH) layers are deposited at a low temperature of 560 degrees C to suppress postgrowth annealing effect that can blueshift emission wavelength of QDs. By introducing annealing processes just after depositing the GaAs spacer layers, the authors demonstrate that the surface morphology of the top GaAs SCH layer can be dramatically improved. For a model structure of five-layer QDs, the surface roughness with the introduced annealing processes (IAPs) is reduced to about 1.3 nm (5x5 mu m(2) area), much less than 4.2 nm without the IAPs. Furthermore, photoluminescence measurements show that inserting the annealing steps does not induce any changes in emission wavelength. This dramatic improvement in surface morphology results from the improved GaAs spacer surfaces due to the IAPs. The technique reported here has important implications for realizing stacked 1.3 mu m InAs/GaAs QD lasers based on MOCVD.

SELF-CONSISTENT TREATMENT OF 3-DIMENSIONAL - 2-DIMENSIONAL AND 2-DIMENSIONAL - 2-DIMENSIONAL RESONANT-TUNNELING IN DOUBLE-BARRIER STRUCTURES

By using a transfer-matrix method on the basis of two-dimensional (2D) Bloch sums in accordance with a tight-binding scheme, a self-consistent calculation on the resonant tunneling in asymmetric double-barrier structures is presented, in which contributions to resonant tunneling from both three-dimensional (3D) electrons in the contacts and 2D electrons in the spacer or accumulation layers are considered simultaneously. The charge buildup effect on the current versus voltage (I-V) curves is evaluated systematically, showing quantitatively how it results in the I-V bistability and enhanced differences between I-V curves for positive and negative bias in an asymmetric double-barrier structure. Special attention is focused on the interaction between 3D-2D and 2D-2D resonant-tunneling processes, including the suppression of 2D-2D resonant tunneling by the charge buildup in the well accompanying the 3D-2D resonant tunneling. The effects of the emitter doping condition (doping concentration, spacer thickness) on the presence of two types of quasi-2D levels in the emitter accumulation layers, and on the formation of a potential bulge in the emitter region, are discussed in detail in relation to the tunneling process.

Capillary electrochromatographic separation of enantiomers on chemically bonded type of cellulose derivative chiral stationary phases with a positively charged spacer

Positively charged chiral stationary phases (CSPs) were prepared for capillary electrochromatography (CEC) separation of enantiomers by chemically immobilizing cellulose derivatives onto diethylenetriaminopropylated silica (DEAPS) with tolylene-2,4-diisocyanate (TDI) as a spacer reagent. Anodic electroosmotic mobility was observed in both nonaqueous and aqueous mobile phases due to the positively charged amines on the surface of the prepared CSPs. For comparison, the traditionally used 3-aminopropyl silica (APS) was also adopted as the base material instead of DEAPS to prepare CSP. It was observed that the EOF on the DEAPS-based CSP was 18%-60% higher than that on the APS-based CSP under nonaqueous mobile phase conditions. Separation of enantiomers in CEC was performed on the positively charged CSPs with the nonaqueous mobile phases of pure ethanol or mixture of hexane-alcohol and the aqueous phases of acetonitrile-water or 95% ethanol. Fast separation of enantiomers was achieved on the newly prepared CSPs.

Synthesis of covalently bonded cellulose derivative chiral stationary phases with a bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate

A bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate (TEPI) was initially adopted as a spacer reagent to prepare the bonded types of chiral stationary phases (CSPs) with cellulose derivatives. The silica-based CSPs were chemically prepared with non-regioselective and regioselective approaches and their chiral resolving capabilities were evaluated in terms of HPLC resolution of test enantiomers. It was observed that the chiral recognition capabilities of the non-regioselectively prepared CSPs were influenced by the amount of TEPI used. And also, the regioselectively prepared CSP generally showed a slightly higher resolution power than the non-regioselectively prepared CSP, while the non-regioselective procedures were highly advantageous to rapid preparation. In addition, chiral recognition of the prepared CSPs was affected by the properties of the used silica matrices. (C) 2003 Elsevier B.V. All rights reserved.

High efficiency and stable dye-sensitized solar cells with an organic chromophore featuring a binary pi-conjugated spacer

We employed a binary spacer of orderly conjugated 3,4-ethyldioxythiophene and thienothiophene to construct a wide-spectral response organic chromophore for dye-sensitized solar cells, exhibiting a high power conversion efficiency of 9.8% measured under irradiation of 100 mW cm(-2) air mass 1.5 global (AM1.5G) sunlight and an excellent stability.

Liquid crystalline and light emitting polyacetylenes: Synthesis and properties of biphenyl-containing poly(1-alkynes) with different functional bridges and spacer lengths

Biphenyl- (Biph-) containing 1-alkynes (3 and 4) and their polymers (1 and 2) with varying bridge groups and spacer lengths were synthesized and the effects of the structural variation on their properties, especially their mesomorphism and photoluminescence behaviors, were studied. The acetylene monomers 3(3) [HCdropC(CH2)(3)O-Biph-OCO(CH2)(10)CH3] and 4(m) [HCdropC(CH2)(m)OCO-Biph-OCO(CH2)(10)-CH3, m = 3, 4] were prepared by sequential etherization and esterification reactions of 1-alkynes. While 3(3) exhibits enantiotropic crystal E and SmB mesophases, its structural cousin 4(3) displays only a monotropic SmB phase. Enantiotropic SmA and SmB mesophases are, however, developed when the spacer length is increased to 4. Polymerizations of the monomers are effected by Mo-, W-, Rh-, and Fe-based catalysts, with the WCl6-Ph4Sn catalyst giving the best results (isolation yield up to 85% and M-w up to 59000). The polymers were characterized by IR, UV, NMR, TGA, DSC, POM, XRD, and PL analyses. Compared to 1(3), 2(3) shows a red-shifted absorption, a higher T-i, and a better packed interdigitated bilayer SmA(d) structure, while the mesophase of 2(4) involves monolayer-packing arrangements of the mesogens. Upon photoexcitation, 1(3) emits almost no light but 2(m) gives a strong ultraviolet emission (lambda(max) similar to 350 nm), whose intensity increases with the spacer length.

An improved PCR method for direct identification of Porphyra (Bangiales, Rhodophyta) using conchocelis based on a RUBISCO intergenic spacer

An improved method of PCR in which the small segment of conchocelis is amplified directly without DNA extraction was used to amplify a RUBISCO intergenic spacer DNA fragment from nine species of red algal genus Porphyra (Bangiales, Rhodophyta), including Porphyra yezoensis (Jiangsu, China), P. haitanensis (Fujian, China), P. oligospermatangia (Qingdao, China), P. katadai (Qingdao, China), P. tenera (Qingdao, China), P. suborboculata (Fujian, China), P. pseudolinearis (Kogendo, Korea), P. linearis (Devon, England), and P. fallax (Seattle, USA). Standard PCR and the method developed here were both conducted using primers specific for the RUBISCO spacer region, after which the two PCR products were sequenced. The sequencing data of the amplicons obtained using both methods were identical, suggesting that the improved PCR method was functional. These findings indicate that the method developed here may be useful for the rapid identification of species of Porphyra in a germplasm bank. In addition, a phylogenetic tree was constructed using the RUBISCO spacer and partial rbcS sequence, and the results were in concordant with possible alternative phylogenies based on traditional morphological taxonomic characteristics, indicating that the RUBISCO spacer is a useful region for phylogenetic studies.

Phylogeography of the Northern Atlantic species Chondrus crispus (Gigartinales, Rhodophyta) inferred from nuclear rDNA internal transcribed spacer sequences

Eighteen isolates of the red algae Chondrus crispus were collected from Northern Atlantic sites, together with C. ocellatus, C. yendoi and C. pinnulatus from the North Pacific. The nuclear rDNA internal transcribed spacer (ITS) was sequenced and compared, spanning both the ITS regions and the 5.8S rRNA gene. Percentage of nucleotide variation for C. crispus ranged from 0.3% to 4.0%. Phylogenetic analyses were performed using maximum parsimony (MP), neighbor-joining (NJ) and minimum evolution methods. They showed that two main clades existed within the C. crispus samples examined and that suggested C. crispus had a single Atlantic origin. The clustering however did not follow the geographic origin. We hypothesized that the current distribution of C. crispus populations might be a result of three main factors: temperature boundaries, paleoclimate and paleoceanography. ITS data exhibited abundant molecular information not only for phylogeographical investigation but also for systematics studies.