Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

Fluorene-Based Copolymers Containing Dinaphtho-s-indacene as New Building Blocks for High-Efficiency and Color-Stable Blue LEDs

By incorporating a new building block, 7,7,15,15-tetraoctyldinaphtho-s-indacene (NSI), into the backbone of poly(9,9-dioctylfluorene) (PFO), a novel series of blue light-emitting copolymers (PFO-NSI) have been developed. The insertion of the NSI unit into the PFO backbone leads to the increase of local effective conjugation length, to form low-energy fluorene-NSI-fluorene (FNF) segments that serve as exciton trapping sites, to which the energy transfers from the high-energy PFO segments. This causes these copolymers to show red-shifted emissions compared with PFO, with a high efficiency and good color stability and purity. The best device performance with a luminance efficiency of 3.43 cd . A(-1), a maximum brightness of 6 539 cd . m(-2) and CIE coordinates of (0.152, 0.164) was achieved.

An Extremely High Molar Extinction Coefficient Ruthenium Sensitizer in Dye-Sensitized Solar Cells: The Effects of pi-Conjugation Extension

We report a heteroleptic ruthenium complex (007) featuring the electron-rich 5-octyl-2,2'-bis(3,4-ethylenedioxythiophene) moiety conjugated with 2,2-bipyridine and exhibiting 10.7% power conversion efficiency measured at the AM1.5G conditions, thanks to the enhanced light-harvesting that is closely related to photocurrent. This C107 sensitizer has an extremely high molar extinction coefficient,of 27.4 x 10(3) M-1 cm(-1) at 559 nm in comparison to its analogue C103 (20.5 x 10(3) M-1 cm(-1) at 550 nm) or Z907 (12.2 x 10(3) M(-1)cm(-1) at 521 nm) with the corresponding 5-hexyl-3,4-ethylenedioxythiopliene- or nonyl-substituted bipyridyl unit. The augmentation of molar extinction coefficients and the bathochromic shift of low-energy absorption peaks along with the pi-conjugation extension are detailed by TD-DFT calculations. The absorptivity of mesoporous titania films grafted with Z907, C103, or C107 sublinearly increases with the molar extinction coefficient of sensitizers, which is consistent with the finding derived from the surface coverage measurements that the packing density of those sensitizers decreases with the geometric enlargement of ancillary ligands.

Improved color purity and efficiency in polyfluorene-based light-emitting diodes

Polyfluorene (PF) is a class of typical blue electroluminescent (EL) material, but it exhibits undesired feature in the green spectral region under operation condition. We investigated the spectral properties of different device structures of poly(9,9-dioctylfluorene) (PFO)-based light-emitting diodes, and found that the interaction between cathode and PFO is the main origination of green emission in EL devices. The general method of inserting a buffer layer between the PFO and cathode can decrease the low energy band emission to purify the color and improve the EL performance of devices.

Tunable photoluminescent and cathodoluminescent properties of ZnO and ZnO : Zn phosphors

ZnO and ZnO: Zn powder phosphors were prepared by the polyol-method followed by annealing in air and reducing gas, respectively. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectra (XPS), electron paramagnetic resonance (EPR), and photoluminescence (PL) and cathodoluminescence ( CL) spectra, respectively. The results indicate that all samples are in agreement with the hexagonal structure of the ZnO phase and the particle sizes are in the range of 1-2 mu m. The PL and CL spectra of ZnO powders annealed at 950 degrees C in air consist of a weak ultraviolet emission band ( similar to 390 nm) and a broad emission band centered at about 527 nm, exhibiting yellow emission color to the naked eyes. When the sample was reduced at the temperatures from 500 to 1050 degrees C, the yellow emission decreased gradually and disappeared completely at 800 degrees C, whereas the ultraviolet emission band became the strongest. Above this temperature, the green emission ( similar to 500 nm) appeared and increased with increasing of reducing temperatures.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Characterization of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii by electrospray ionization tandem mass spectrometry

The fragmentation mechanism of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii (FAK) was investigated using electrospray ionization tandem mass spectrometry (ESI-MSn) firstly. The analysis of the collision-induced dissociation (CID) spectra of three purified aconitine standards and six previously reported aconitines indicated that the fragmentation of the protonated aconitines at low-energy CID follows a similar pathway. The elimination of a C-8-substituent such as an acetic acid or a fatty acid is the dominant fragmentation mode in MS2. Successive losses of CH3COOH, CH3OH, H2O, BzOH, and CO are the main fragmentation pathways of aconitine-type alkaloids in MS3 spectra. Based on these features, a rapid method for the direct detection and characterization of alkaloids from an ethanolic extract of FAK is described. All the known aconitum alkaloids are detected and a series of lipo-aconitines has been found for the first time in this plant.

A study of resonance electron capture ionization on a quadrupole tandem mass spectrometer

Procedures that allow the realization of resonance electron capture (REC) mode on a commercial triple-quadrupole mass spectrometer, after some simple modifications, are described, REC mass spectrometry (MS) and tandem mass spectrometry (MS/MS) experiments were performed and spectra for some compounds were recorded. In particular, the charge-remote fragmentation (CRF) spectra of [M - H](-) ions of docosanoic and docosenoic acids under low-energy collisionally activated dissociation (CAD) conditions were obtained, and showed that there were no significant differences for [M - H](-) ions produced at different resonances (i,e. for [M - H](-) ions with different structures). This observation was explained on the basis of results obtained from deuterium-labeled fatty acids, which showed that different CRF ions (but with the same m/z value in the absence of labels) could be produced by different mechanisms, and all of them were obviously realized under CAD conditions that made spectra practically indistinguishable. The other example, which compared the REC-MS/MS spectrum of [M - H](-) ions and EI-MS/MS spectrum of M+. ions of daidzein, demonstrated the potential of the REC-MS/MS technique for more complex structure elucidation. Copyright (C) 2000 John Wiley & Sons, Ltd.

Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

低能髙流强电子束在绝缘管中的导向效应研究

带电粒子与绝缘体表面相互作用的研究揭示了很多新的物理现象和物理规律，目前该研究领域已拓展到原子物理，固体物理，等离子体物理等领域，特别是促进了纳米材料，超小尺寸半导体芯片制作，固体结构分析等应用领域的发展。本论文介绍了低能高流强电子束与绝缘体相互作用实验平台的建设，包括强流LaB6电子枪，64通道一维位置灵敏法拉第筒，电流电压转换放大器，基于Lab VIEW的数据获取软件系统等。研究了低能高流强电子束与锥形绝缘毛细管之间的相互作用。测量了出射电子的角分布与能谱，研究了入射电子能量、流强对电子传输效率的影响，分析了电子与高电荷态粒子同毛细管相互作用的区别。用低能高流强电子束与等内径弯曲绝缘管相互作用，测量了出射电子的角分布，研究了入射能量与流强对导向效应的影响。研究表明，与高点和态离子相比，电子与绝缘管相互作用有许多新的特性，电子传输效率较高电荷态粒子小1-2个数量级，且能量损失严重。量子反射和多次小角度散射是电子导向的主要原因

Modern sedimentary environments and dynamic depositional systems in the southern Yellow Sea

Based on analyses of more than 600 surface sediment samples together with large amounts of previous sedimentologic and hydrologic data, the characteristics of modern sedimentary environments and dynamic depositional systems in the southern Yellow Sea (SYS) are expounded, and the controversial formation mechanism of muddy sediments is also discussed. The southern Yellow Sea shelf can be divided into low-energy sedimentary environment and high-energy sedimentary environment; the low-energy sedimentary environment can be further divided into cyclonic and anticyclonic ones, and the high-energy environment is subdivided into high-energy depositional and eroded environments. In the shelf low-energy environments, there developed muddy depositional system. In the central part of the southern Yellow Sea, there deposited the cold eddy sediments under the actions of a meso-scale cyclonic eddy (cold eddy), and in the southeast of the southern Yellow Sea, an anticyclonic eddy muddy depositional system (warm eddy sediment) was formed. These two types of sediments showed evident differences in grain size, sedimentation rate, sediment thickness and mineralogical characteristics. The high-energy environments were covered with sandy sediments on seabed; they appeared mainly in the west, south and northeast of the southern Yellow Sea. In the high-energy eroded environment, large amounts of sandstone gravels were distributed on seabed. In the high-energy depositional environment, the originally deposited fine materials (including clay and fine silt) were gradually re-suspended and then transported to a low-energy area to deposit again. In this paper, the sedimentation model of cyclonic and anticyclonic types of muddy sediments is established, and a systematic interpretation for the formation cause of muddy depositional systems in the southern Yellow Sea is given.

泥河湾盆地磁性地层学研究——以东谷索和岑家湾剖面为例

The Nihewan Basin is a key area for research into human occupation at high northern latitudes in northeast Asia after the initial expansion of early humans out of Africa. Well-developed late Cenozoic lacustrine deposit sequence in this basin offers a unique opportunity to address this issue. In this thesis, detailed magnetostratigraphic investigation coupled with mineral magnetism was conducted on the Donggutuo and Cenjiawan sections in the eastern basin, where lacustrine deposits sequences containing the Donggutuo, Maliang and Cenjiawan Paleolithic sites are well developed. The sequences are mainly composed of grayish-white clays, grayish-green clayey silts, grayish-yellow silts and fine-grained brown sands, which have recorded reliable polarity variations of geomagnetic field.Characteristics of the anisotropy of magnetic susceptibility show that the sediments have preserved typical original magnetic fabric for sediments, indicating that the strata were developed in a low-energy lake environment and were never perturbed by tectonic stress since deposition. High-temperature magnetic susceptibility measurements (x-T) of representative specimens and demagnetization experiments indicate that the dominant magnetic mineral and remanent carrier at the two sections is magnetite. In addition, hematite and possibly minor maghemite exists in some portions of the sequences. The majority of the samples have relatively simple demagnetization behaviors. After removal of soft magnetic components, the stable characteristic remanent magnetizations (ChRMs) are isolated, which can represent the original remanences.The Donggutuo section mainly records the Brunhes chron, the Matuyama chron and the Jaramillo subchron. The Maliang stone artifact layer occurs just below the Brunhes/Matuyama boundary; and the Donggutuo artifact layer, just below the Jaramillo onset. Accordingly, the Maliang and Donggutuo sites can be dated at about 0.78 Ma and 1.1 Ma, respectively. The Cenjiawan section has recorded a portion of the Matuyama chron. After correlations with the magnetic polarity sequence of the Majuangou section adjacent to this section, the Cenjiawan stone artifact layer is determined below the Jaramillo onset, with an estimated age of 1.1 Ma.To establish the magnetic stratigraphy framework for the lacustrine sediments in the eastern Nihewan Basin, this thesis draws on the magnetic polarity sequences of the Donggutuo and Cenjiawan sections as well as previously obtained results from the Majuangou, Haojiatai, Xiaochangliang and Donggou sections for magnetostratigraphic correlations. The accumulation of the lacustrine sequences at the east margin of the basin commenced from about 2.0 Ma. These sequences record not only the coarse magnetostratigraphy of the Brunhes normal chron and the middle to late Matuyama reverse chron (that is, the Jaramillo and Olduvai subchrons) but also some of the fine structure (that is, the Kamikatsura, Santa Rosa, Punaruu and Cobb Mountain geomagnetic events). The development of the Nihewan paleolake experienced at least twice large expansion periods, split by a large-scale shrinking event in the middle period of the paleolake development. The accumulation of the lacustrine strata was controlled by fault activities.After temporal control for the Donggutuo, Maliang and Cenjiawan Paleolithic sites were established, the three sites along with other well-dated Paleolithic/hominin sites of the Early Pleistocene in North China were combined to construct a chronological sequence of early human occupation in northeastern Asia. Furthermore, after incorporation of paleoclimate changes retrieved from Chinese loess/paleosol sequences and marine sediments, it could be possibly proposed that human groups of the Early Pleistocene in North China might have survived repeated warm/humid interglacials and cold/dry glacials, which were paced by earth orbital variations of the Eastern paleomonsoon.

Structure and properties of samarium overlayer and Sm/Rh surface alloy on Rh(100)

The structure and properties of Sm overlayer and Sm/Rh surface alloy have been investigated with Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption spectroscopy (TDS). The growth of Sm on Rh(100) at room temperature (RT) appears following the Stranski-Krastanov growth mode and only the trivalent state Sm is observed from XPS results. Thermal treatment of the Sm film at 900 K leads to the formation of ordered surface alloy which shows the c(5 root2 x root2)R45 degrees and c(2 x 2) LEED patterns. Annealing the Sm film at temperature above 400 K makes the binding energy (B.E.) of Sm 3d(5/2) shift to higher energy by 0.7 eV, which indicates charge transfer from Sm to Rh(100) substrate, causing the increase of CO desorption temperature.

Dedicated global optimization search for ground state silica nanoclusters: (SiO2)(N) (N=6-12)

Flikkema, E., & Bromley, S. T. (2004). Dedicated global optimization search for ground state silica nanoclusters: (SiO2)(N) (N=6-12). Journal of Physical Chemistry B, 108 (28), 9638-9645. RAE2008

Palaeontology of the Middle Turonian limestones of the Nysa Kłodzka Graben (Sudetes, SW Poland): biostratigraphical and palaeogeographical implications

The ammonites Lewesiceras peramplum Mantell and ?Lewesiceras sp. are reported from the Upper Cretaceous in the Nysa Kłodzka Graben; they date from the Middle Turonian and ?Coniacian, respectively. The Middle Turonian limestones of the Stara Bystrzyca quarry contain an abundant assemblage of inoceramids (Inoceramus cuvieri Sowerby and I. lamarcki Parkinson) and other bivalves, including oysters, as well as brachiopods and trace fossils. Micropalaeontological data show the presence of foraminifers and siliceous sponge spiculae, bryozoans, ostracods and fragments of bivalves and gastropods. The Middle Turonian calcareous deposits belongs to the upper part of the Inoceramus lamarcki Zone (late Middle Turonian) and were deposited on a shallow, subtidal offshore shelf. They overlie the Middle Turonian Bystrzyca and Długopole Sandstones, which represent foreshore-shoreface delta deposits. The fossil assemblage suggests a moderate- to low-energy, normal-salinity environment with occasionally an oxygen deficit.