Synthesis and characterization of high molecular weight polyaniline for organic electronic applications

High molecular weight polyaniline (PANI) was synthesized by a combined procedure incorporating various synthesis methods. Temperature and open circuit potential of the reaction mixture were collected to monitor the reaction progress. The polymer is characterized by various techniques including gel permeation chromatography, dynamic light scattering, infrared spectroscopy, solid-state nuclear magnetic resonance, and differential scanning calorimetry for elucidating the molecular architecture obtained by this method. As-synthesized PANI was found to possess high molecular weight, reduced branching, reduced cross-linking, and to predominantly consist of linear polymer chains. This polymer was also found to be more stable in solution form. JV characteristics of as-synthesized PANI films indicate a high current density which is due to increased free pathways and less traps for the charge transport to occur in PANI films. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers

The organometallic chemistry of the Ru(001) surface

The organometallic chemistry of the hexagonally close-packed Ru(001) surface has been studied using electron energy loss spectroscopy and thermal desorption mass spectrometry. The molecules that have been studied are acetylene, formamide and ammonia. The chemistry of acetylene and formamide has also been investigated in the presence of coadsorbed hydrogen and oxygen adatoms.

Acetylene is adsorbed molecularly on Ru(001) below approximately 230 K, with rehybridization of the molecule to nearly sp^3 occurring. The principal decomposition products at higher temperatures are ethylidyne (CCH_3) and acetylide (CCH) between 230 and 350 K, and methylidyne (CH) and surface carbon at higher temperatures. Some methylidyne is stable to approximately 700 K. The preadsorption of hydrogen does not alter the decomposition products of acetylene, but reduces the saturation coverage and also leads to the formation of a small amount of ethylene (via an η^2-CHCH_2 species) which desorbs molecularly near 175 K. Preadsorbed oxygen also reduces the saturation coverage of acetylene but has virtually no effect on the nature of the molecularly chemisorbed acetylene. It does, however, lead to the formation of an sp^2-hybridized vinylidene (CCH_2) species in the decomposition of acetylene, in addition to the decomposition products that are formed on the clean surface. There is no molecular desorption of chemisorbed acetylene from clean Ru(001), hydrogen-presaturated Ru(001), or oxygen-presaturated Ru(001).

The adsorption and decomposition of formamide has been studied on clean Ru(001), hydrogen-presaturated Ru(001), and Ru(001)-p(1x2)-O (oxygen adatom coverage = 0.5). On clean Ru(001), the adsorption of low coverages of formamide at 80 K results in CH bond cleavage and rehybridization of the carbonyl double bond to produce an η^2 (C,O)-NH_2CO species. This species is stable to approximately 250 K at which point it decomposes to yield a mixture of coadsorbed carbon monoxide, ammonia, an NH species and hydrogen adatoms. The decomposition of NH to hydrogen and nitrogen adatoms occurs between 350 and 400 K, and the thermal desorption products are NH_3 (-315 K), H_2 (-420 K), CO (-480 K) and N_2 (-770 K). At higher formamide coverages, some formamide is adsorbed molecularly at 80 K, leading both to molecular desorption and to the formation of a new surface intermediate between 300 and 375 K that is identified tentatively as η^1(N)-NCHO. On Ru(001)- p(1x2)-O and hydrogen-presaturated Ru(001), formamide adsorbs molecularly at 80 K in an η^1(O)- NH_2CHO configuration. On the oxygen-precovered surface, the molecularly adsorbed formamide undergoes competing desorption and decomposition, resulting in the formation of an η^2(N,O)-NHCHO species (analogous to a bidentate formate) at approximately 265 K. This species decomposes near 420 K with the evolution of CO and H_2 into the gas phase. On the hydrogen precovered surface, the Η^1(O)-NH_2CHO converts below 200 K to η^2(C,O)-NH_2CHO and η^2(C,O)-NH^2CO, with some molecular desorption occurring also at high coverage. The η^2(C,O)-bonded species decompose in a manner similar to the decomposition of η^2(C,O)-NH_2CO on the clean surface, although the formation of ammonia is not detected.

Ammonia adsorbs reversibly on Ru(001) at 80 K, with negligible dissociation occurring as the surface is annealed The EEL spectra of ammonia on Ru(001) are very similar to those of ammonia on other metal surfaces. Off-specular EEL spectra of chemisorbed ammonia allow the v(Ru-NH_3) and ρ(NH_3) vibrational loss features to be resolved near 340 and 625 cm^(-1), respectively. The intense δ_g (NH_3) loss feature shifts downward in frequency with increasing ammonia coverage, from approximately 1160 cm^(-1) in the low coverage limit to 1070 cm^(-1) at saturation. In coordination compounds of ammonia, the frequency of this mode shifts downward with decreasing charge on the metal atom, and its downshift on Ru(001) can be correlated with the large work function decrease that the surface has previously been shown to undergo when ammonia is adsorbed. The EELS data are consistent with ammonia adsorption in on-top sites. Second-layer and multilayer ammonia on Ru(001) have also been characterized vibrationally, and the results are similar to those obtained for other metal surfaces.

Discovery of non-zero neutrino mixing angle θ_13 using Daya Bay antineutrino detectors

The Daya Bay Reactor Antineutrino Experiment observed the disappearance of reactor $\bar{\nu}_e$ from six $2.9~GW_{th}$ reactor cores in Daya Bay, China. The Experiment consists of six functionally identical $\bar{\nu}_e$ detectors, which detect $\bar{\nu}_e$ by inverse beta decay using a total of about 120 metric tons of Gd-loaded liquid scintillator as the target volume. These $\bar{\nu}_e$ detectors were installed in three underground experimental halls, two near halls and one far hall, under the mountains near Daya Bay, with overburdens of 250 m.w.e, 265 m.w.e and 860 m.w.e. and flux-weighted baselines of 470 m, 576 m and 1648 m. A total of 90179 $\bar{\nu}_e$ candidates were observed in the six detectors over a period of 55 days, 57549 at the Daya Bay near site, 22169 at the Ling Ao near site and 10461 at the far site. By performing a rate-only analysis, the value of $sin^2 2\theta_{13}$ was determined to be $0.092 \pm 0.017$.

Obtenção do copolímero de acrilonitrila e vinil-imidazol a partir da modificação química da poliacrilonitrila

Polímeros contendo anéis heterocíclicos, como o imidazol, possuem um grande interesse comercial e científico devido ao seu emprego em diversas áreas. Esses polímeros podem ser obtidos pela modificação química de polímeros comerciais como a poliacrilonitrila. Geralmente, esse tipo de reação é realizada por aquecimento convencional (térmico). Entretanto, mais recentemente, a irradiação por micro-ondas também começou a ser utilizada como fonte de energia para esse fim. Nesta Dissertação foi estudada, comparativamente, a modificação química da poliacrilonitrila comercial com etilenodiamina sob ativação de P2S5, empregando como fonte de aquecimento: o método convencional (térmico) e irradiação de micro-ondas, geradas em forno de micro-ondas doméstico e em reator de micro-ondas (Discover CEM), para produzir o copolímero de poliacrilonitrila e 2-vinil-imidazol. As reações foram efetuadas em diferentes tempos reacionais, em diferentes temperaturas no reator de micro-ondas e em diferentes potências do forno doméstico. Os copolímeros produzidos foram caracterizados por espectroscopia na região do infravermelho (FTIR) e por ressonância magnética de núcleo de hidrogênio (NMR-1H). A poliacrilonitrila foi modificada quimicamente com sucesso em todos os métodos empregados, como foi verificado pela sua análise de FTIR. Os melhores resultados obtidos foram: em 48 h de aquecimento térmico, 20 min de irradiação de micro-ondas em forno doméstico e 20 min a 80C em reator de micro-ondas, no entanto todas as análises indicaram uma derivatização abaixo de 10 %

Estudo da reação entre o metanol e o acetato de etila em catalisadores Mg/La por espectroscopia no infravermelho acoplada a espectrometria de massas

A transesterificação metílica em meio homogêneo é catalisada por bases, tais como hidróxidos e alcóxidos de sódio ou potássio e se processa em baixa temperatura de reação, mesmo em escala industrial. A utilização de catalisadores formados por sólidos básicos aparece como uma alternativa promissora aos processos homogêneos convencionais, tendo em vista as inúmeras vantagens como a redução da ocorrência das reações indesejáveis de saponificação e redução de custos dos processos pela diminuição do número de operações associadas. Em estudos anteriores realizados pelo grupo, catalisadores a base de Mg/La com diferentes composições químicas (9:1, 1:1 e 1:9) mostraram-se promissores para a obtenção de ésteres metílicos via reação de transesterificação, porém não foi possível fazer uma correlação entre atividade catalítica e as propriedades físico-químicas quando toda a série foi considerada. Assim, a realização de um estudo de caráter fundamental, baseado em reações modelo e uso de moléculas sonda, permite avançar no entendimento das propriedades de superfície destes catalisadores. Portanto, o presente trabalho estuda a reação entre metanol e acetato de etila em catalisadores a base de Mg/La utilizando espectroscopia de reflectância difusa no infravermelho com transformada de Fourier (DRIFTS) acoplada a espectrometria de massas (MS) identificando os intermediários e produtos formados para determinar a rota reacional. As análises de difração de raios X mostram que os precursores são predominantemente compostos por carbonatos hidratados de magnésio (Mg/La 1:1 e 9:1) e de lantânio (Mg/La 1:9). Os perfis de decomposição térmica e difratogramas de raios X obtidos a partir de tratamento térmico in situ indicaram que estes carbonatos se decompõem apenas a partir de 750 C. As análises de Dessorção a Temperatura Programada realizadas com moléculas sonda, metanol e acetato de etila, mostraram a adsorção em maior quantidade do metanol independente da composição química do sólido. A partir dos resultados obtidos por DRIFTS-MS foi proposta uma rota reacional para a reação de transesterificação do acetato de etila e metanol, que ocorre via adsorção do metanol e do acetato de etila na superfície do catalisador, seguida da formação de um intermediário tetraédrico formado pelas moléculas adsorvidas, que sofre um rearranjo formando etanol, acetato de metila, acetona e metano. Simultaneamente, parte do metanol adsorvido como metoxi monodentado é desidrogenado formando formiatos que são dessorvidos na forma de formaldeído e decompostos formando CO2 e H2

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.

Heavily doped polycrystalline 3C-SiC growth on SiO2/Si(100) substrates for resonator applications

3C-SiC is a promising material for the development of microelectromechanical systems (MEMS) applications in harsh environments. This paper presents the LPCVD growth of heavily nitrogen doped polycrystalline 3C-SiC films on Si wafers with 2.0 mu m-thick silicon dioxide (SiO2) films for resonator applications. The growth has been performed via chemical vapor deposition using SiH4 and C2H4 precursor gases with carrier gas of H-2 in a newly developed vertical CVD chamber. NH3 was used as n-type dopant. 3C-SiC films were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS), and room temperature Hall Effect measurements. It was shown that there is no voids at the interface between 3C-SiC and SiO2. Undoped 3C-SiC films show n-type conduction with resisitivity, Hall mobility, and carrier concentration at room temperature of about 0.56 Omega center dot cm, 54 cm(2)/Vs, and 2.0x 10(17) cm(-3), respectively. The heavily nitrogen doped polycrystalline 3C-SiC with the resisitivity of less than 10(-3) Omega center dot cm was obtained by in-situ doping. Polycrystalline SiC resonators have been fabricated preliminarily on these heavily doped SiC films with thickness of about 2 mu m. Resonant frequency of 49.1 KHz was obtained under atmospheric pressure.

Microstructure studies of PdGe/Ge ohmic contacts to n-type GaAs formed by rapid thermal annealing

A low resistance and shallow ohmic contact to n-GaAs is performed by using Ge/Pd/GaAs trilayer structure and rapid thermal annealing process. The dependence of specific contact resistivity on the temperature of rapid thermal annealing is investigated. A good ohmic contact is formed after annealing at 400-500 degrees C for 60 s. The best specific contact resistivity is 1.4 x 10(-6) Omega cm(2). Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS) and scanning electron microscopy (SEM) are used to analyze the interfacial microstructure. A strong correlation between the contact resistance and the film microstructure is observed.

Low-lying states of heavy nuclei within the nucleon pair approximation

In this article we perform systematic calculations on low-lying states of 33 nuclei with A=202-212, using the nucleon pair approximation of the shell model. We use a phenomenological shell-model Hamiltonian that includes single-particle energies, monopole and quadrupole pairing interactions, and quadrupole-quadrupole interactions. The building blocks of our model space include one J=4 valence neutron pair, and one J=4,6,8 valence proton pair, in addition to the usual S and D pairs. We calculate binding energies, excitation energies, electric quadrupole and magnetic dipole moments of low-lying states, and E2 transition rates between low-lying states. Our calculated results are reasonably consistent with available experimental data. The calculated quadrupole moments and magnetic moments, many of which have not yet been measured for these nuclei, are useful for future experimental measurements.

Transport parameters in neutron stars from in-medium N N cross sections

We present a numerical study of shear viscosity and thermal conductivity of symmetric nuclear matter, pure neutron matter, and beta-stable nuclear matter, in the framework of the Brueckner theory. The calculation of in-medium cross sections and nucleon effective masses is performed with a consistent two- and three-body interaction. The investigation covers a wide baryon density range as needed in the applications to neutron stars. The results for the transport coefficients in beta-stable nuclear matter are used to make preliminary predictions on the damping time scales of nonradial modes in neutron stars.

核质量测量与Schottky探针研究

本文研究了用于九五国家大科学工程“兰州重离子加速器冷却储存环HIRFL-CSR”上的Schottky探针及利用schottky质谱仪进行核质量测量，研究了当前国际上核质量测量研究方法并结合当前的核质量测量研究现状，根据CSR能提供的实验条件，研究认为在HIRFL-CSR上利用Schttkv质谱仪方法进行核质量测量有很广阔的前景。根据HIRFL-CSR束流参数和束诊要求，设计了schottky探针电极及超高真空Schottky探针安装靶室。利用三维电磁场模拟计算程序MAFIA优化了Schottky探针的结构和形状。通过改变电极板的边缘场矫正板的长度和角度，在极板间获得了最佳的场分布。模拟结果表明对水平和垂直方向的探针矫正板长度分别为4cm、3cm并且夹角分别为30、20度时在探针极板间可得到很好的横向匀场。对Schottky样机的信号响应进行的仔细的测试，获得了较满意的结果。本文还研究了利用Schottky质谱仪进行核质量测量的Schottky信号处理方法与质量测量原理，对当前远离β稳定线的核质量测量前景做了仔细分析。对Schottky探针用于CSR的束流参数测量和核质量测量方法进行了较深入的探讨。

Role of Landau quantization on the neutron-drip transition in magnetar crusts

The role of a strong magnetic field on the neutron-drip transition in the crust of a magnetar is studied. The composition of the crust and the neutron-drip threshold are determined numerically for different magnetic field strengths using the experimental atomic mass measurements from the 2012 Atomic Mass Evaluation complemented with theoretical masses calculated from the Brussels-Montreal Hartree-Fock-Bogoliubov nuclear mass model HFB-24. The equilibrium nucleus at the neutron-drip point is found to be independent of the magnetic field strength. As demonstrated analytically, the neutron-drip density and pressure increase almost linearly with the magnetic field strength in the strongly quantizing regime for which electrons lie in the lowest Landau level. For weaker magnetic fields, the neutron-drip density exhibits typical quantum oscillations. In this case, the neutron-drip density can be either increased by about 14% or decreased by 25% depending on the magnetic field strength. These variations are shown to be almost universal, independently of the nuclear mass model employed. These results may have important implications for the physical interpretation of timing irregularities and quasiperiodic oscillations detected in soft gamma-ray repeaters and anomalous x-ray pulsars, as well as for the cooling of strongly magnetized neutron stars.

Kinestatin: a novel bradykinin B2 receptor antagonist peptide from the skin secretion of the Chinese toad, Bombina maxima

We have isolated a novel bradykinin B2-receptor antagonist peptide, kinestatin, from toad (Bombina maxima) defensive skin secretion. Mass spectroscopy established a molecular mass of 931.56 Da and a provisional structure: pGlu-Leu/Ile-Pro-Gly-Leu/Ile-Gly-Pro-Leu/Ile-Arg.amide. The unmodified sequence, -QIPGLGPLRG-, was located at the C-terminus of a 116-amino-acid residue open-reading frame following interrogation of a sequenced B. maxima skin cDNA library database. This confirmed the presence of appropriate primary structural attributes for the observed post-translational modifications present on the mature peptide and established residue 2 as Ile and residues 5/8 as Leu. Kinestatin represents a prototype novel peptide from amphibian skin.

Apc(MIN) modulation of vitamin D secosteroid growth control

A central paradox of vitamin D biology is that 1alpha,25-(OH)(2) D(3) exposure inversely relates to colorectal cancer (CRC) risk despite a capacity for activation of both pro- and anti-oncogenic mediators including osteopontin (OPN)/CD44 and E-cadherin, respectively. Most sporadic CRCs arise from adenomatous polyposis coli (APC) gene mutation but understanding of its effects on vitamin D growth control is limited. Here we investigate effects of the Apc(Min/+) genotype on 1alpha,25-(OH)(2) D(3) regulation of OPN/CD44/E-cadherin signalling and intestinal tumourigenesis, in vivo. In untreated Apc(Min/+) versus Apc(+/+) intestines, expression levels of OPN and its CD44 receptor were increased, whereas E-cadherin tumour suppressor signalling was attenuated. Treatment by 1alpha,25-(OH)(2) D(3) or rationally designed analogues (QW or BTW) enhanced OPN but inhibited expression of CD44, the OPN receptor implicated in cell growth. These treatments also enhanced E-cadherin tumour suppressor activity, characterized by inhibition of beta-catenin nuclear localization, T-cell factor 1 and c-myelocytomatosis protein expression in Apc(Min/+) intestine. All secosteroids suppressed Apc(Min/+)-driven tumourigenesis although QW and BTW had lower calcium-related toxicity. Taken together, these data indicate that the Apc(Min/+) genotype modulates vitamin D secosteroid actions to promote functional predominance of E-cadherin tumour suppressor activity within antagonistic molecular networks. APC heterozygosity may promote favourable tissue- or tumour-specific conditions for growth control by vitamin D secosteroid treatment.